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Computational insights into the origins of Z- and enantioselective asymmetric ring-opening/cross-metathesis reactions catalyzed by a sterogenic-AT-RU-complex

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Title:
Computational insights into the origins of Z- and enantioselective asymmetric ring-opening/cross-metathesis reactions catalyzed by a sterogenic-AT-RU-complex
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Nelson, John William ( author )
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Denver, CO
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University of Colorado Denver
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English
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1 electronic file (332 pages). : ;

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Enantioselective catalysis ( lcsh )
Analytical biochemistry ( lcsh )
Chemistry ( lcsh )
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bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

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Review:
Density functional theory (DFT) calculations (B3LYP and M06) were performed to elucidate the mechanism of a Z-selective asymmetric ring-opening/cross-metathesis reaction catalyzed by a ruthenium complex with an N-heterocyclic carbine (NHC)-adamantyl chelator (1cat). The reaction was also enantioselective because the catalyst employed was a chiral and stereogenic at the ruthenium center. The systems that have been computed are without any simplification the catalyst (1cat), allyl acetate substrate, cyclobutene derivative, and one norbornene substrate. A truncated model for a second norbornene derivative was also utilized. The initial metathesis of 1cat with terminal olefins via a side-bound pathway yields two active catalytic species, which lead to the final Z- and E-products, respectively. The high enantioselective excess of both Z- and E-isomers of norbornene derivatives originates from the steric hindrance imparted by the incoming substrate, which only has one favorable approach out of four possible orientations. A low enantiomeric excess observed for E-products in the reaction of cyclobutene is caused by two energetically feasible approaches to the E-active catalyst.
Thesis:
Thesis (M.S.)--University of Colorado Denver. Department of Chemistry
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Includes bibliographic references.
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System requirements: Adobe Reader.
Statement of Responsibility:
by John William Nleosn, Jr.

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|University of Colorado Denver
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Auraria Library
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912558200 ( OCLC )
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COMPUTATIONAL INSIGHTS INTO THE ORIGINS OF Z AND ENANTIOSELCETIVE ASYMMETRIC RING OPENING/CROSS METATHEIS REACTIONS CATALYZED BY A STEREOGENIC AT RU COMPLEX by J OHN WILLIAM NELSON JR. B.S., University of Colorado Denver, 2014 A thesis submitted to the University of Colorado Denver in partial fulfillment of the requirements for the degree of Masters of Science Chemistry 2015

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ii This thesis for the Masters of Science degree by John William Nelson Jr. has been approved for the Chemistry Program by X ia otai Wang Scott Reed Hai Lin April 21, 2015

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iii Nelson Jr., John William ( M.S. Chemistry ) Computational Insights into the Origins of Z and Enantioselective Asymmetric Ring Opening/ Cross Metathesis Reactions Catalyzed by a Stereogenic at Ru Complex Thesis directed by Associate Professor Xiaotai Wang ABSTRACT Density functional theory (DFT) calculations (B3LYP and M06) were performed to elucidate the mechanism of a Z selective asymmetric ring opening/cross metathesis reaction catalyzed by a ruthenium complex with an N heterocyclic carbene (NHC) adamantyl chelat or ( 1cat ). The reaction was also enantioselective because the catalyst employed was chiral and stereogenic at the ruthenium center. The system s that have been computed are without any simplification the catalyst ( 1cat ) allyl acetate substrate, cyclobutene derivative and one norborn ene substrate. A truncated model for a second norbornene derivative was also utilized The initial metathesis of 1cat with terminal olefins via a side bound pathway yields two active catalytic species, which lead to the final Z and E products, respectively. The high enantioselective excess of both Z and E isomers of norbornene derivatives originates from the steric hindrance imparted by the incoming substrate, which only has one favorable approach out of four possible orientati ons A low enantiomeric excess observed for E products in the reaction of cyclobutene is caused by two energetically feasible approaches to the E active catalyst. The form and content of this abstract are approved. I recommend its publication. Approved: X iaotai Wang

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iv ACKNOWLEDGEMENT I would like to thank my advisor, Dr. Wang, for giving me the opportunity to join his research group. He allowed me the freedom to explore and provided a great learning environment. I would also like to thank the other chemistry students that work in the c omputational lab for aiding in the development of ideas and making it an enjoyable place to work Lastly, I would like to thank my partner for understanding my lack of free time and asking about my day, even though she admittedly has no clue about what I a m talking about.

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v T ABLE OF CONTENTS CHAPTER I. INTRODUCTION ... 1.1 Carbon Carbon Bond Forming R eactions .. 1 1.2 Olefin Metathesis M echanism 1 4 6 1.5 Grubbs Hoveyda C ........ 1 1 1.6 Stereo and Enantioselective C 12 1.7 Role of Olefin M 16 II DENSITY FUNCTIONAL THEORY .. 18 2.1 Theory, Functionals, and M odels of D ensity F unctional T 18 2.2 Computational M 22 2.3 The System s Under I 24 III CROSS METATHESIS OF NORBORNENE DERIVATIVES WITH ALLYL ACETATE SUBSTRATE .. 26 3.1 Initiation with 2 Propen 1 yl Ester Acetic Acid ( A llyl A cetate ) T o Y ield Z and E Active C atalytic S pecies 7 and 4E 26

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vi 3.2 Coupling of 5,6 exo D imet hylbicyclo[2.2.1] hept 2 ene (N orbornene) with C omplex es 7 and 4E 29 3.3 Releas e of Z N orbornene P rodu ct and R e generation of Complexes 7 and 4E ... 4 3.4 Release of E N orbornene P roduct and R egeneration of Complexes 7 and 4E 36 3.5 Coupling of B icyclo[2.2.1] hept 2 ene, (7 anti ) [4 (trifluoromethyl) phenoxy] ( N orbornene*) with C omplex 7 and 4E 38 3.6 Release of Z N orbornene* Product and R egene ration of Complex es 7 and 4E 42 3.7 Release of E N orbornene* Product and Regeneration of Complexes 7 and 4E 4 3 3.8 Turnover L imiting Steps in the AROCM of Norbornene D erivatives 4 4 IV C ROSS METATHESIS OF CYCLOBUTENE DERIVATIVE WITH ALLYL ACETATE 48 4.1 Coupling of ( S R ) 1, 2 D ibenzyloxy 3 cyclobutene to C omplex 7 ... 8 4.2 Coupling of ( S R ) 1, 2 D ibenzyloxy 3 cyclobutene to C omplex 4E .. 4.3 Release of the C yclobutene Z CB P roduct and R egeneration of Complex es 7 and 4E 5 4 4.4 Release of the C yclobutene E CB P roduct and Regeneration of C omplex es 7 and 4E 56 4. 5 Turnover L imiting Steps in the AROCM of Cyclobutene 8 V C ONCLUSION .

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vii 5.1 Conclusion .61 REFERENCES 6 4 APPENDIX A. Full S chemes and E xtra F igures ... 68 B Cartesian Coordinates (), SCF Energies and Free Energies at 298.15 K and 1 atm for the Optimized Structures

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1 CHAPTER I INTRODUCTION 1.1 Carbon Carbon B ond F orming R eactions Reactions that result in the formation o f carbon carbon bonds are a desirable synthetic tool for chemists based on the utility of these bonds in our everyday world. This is evident from the many reactions named after chemists who have won the Nobel Prize in Chemistry, such as the Diels Alder reaction (Nobel Prize in 1950 1 ) and the Grignard reaction ( Nobel Prize in 1912 2 ) Further developments have been achieved in carbon carbon double and triple bond forming rea ctions In 2005 the Nobel Prize in Chemistry was awarded to Yves Chauvin, Robert H. Grubbs, and Richard R. S chrock for their development and understanding of olefin metathesis and its catalysts 3 Olefin (a molecule containing a carbon carbon double bond) metathesis (meaning to switch or transpose something) is the rearrangement of carbon carbon double bonds The development of these catalysts with transition metal (TM) centers aided in a reduction of waste and unwanted by products in the synthesis of C=C bonds and has gained growing popularity and synthetic use over the past two and a half decades 1.2 Olefin Metathesis M echanism Yves Chauvin contribution to olefin metathesis was explaining t he reaction mechanism and the role of the catalyst Chauvin pieced together three separate events that were all published in 1964 : 4 (i) The D isprop ortionation of Olefins Catalyzed by a M olybdenum or T ungsten based Heterogeneous Catalyst Deposited on A lumina by R.L. Banks of Phillips Petroleum, 5 (ii) The H omogeneous C atalysis of P olymerization of

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2 C yclopentene by R ing O pening by G. Natta 6 and (iii) T he E xistence of a N ew M etal C arbon B on d, T he C arbenes of E.O. Fischer. 7 Chauvin realized that these seemingly disparate reactions were connected From these papers, he proposed a reaction mechanism that was based on a [2 + 2] cycloaddition/cycloreversion manifold T he metal center is bound to a carbon atom through a double bond forming a carbene complex (M=C H R 1 ) and an incoming terminal olefin molecule ( H 2 C=C H R 2 ) coordinates to the metal center The resulting structure is a four membered metallacycl obutane ring 8 The reaction then proceed s by forming a new carbene complex (M=CH 2 ) through cycloreversion, which also releas es the R 1 H C=C H R 2 molecule ( Figure 1 a ). Figure 1 a) General reaction scheme for olefin metathesis reactions. b) General reac tion scheme for asymmetric ring opening/cross metathesis reactions Many chemists attempted to prove/disprove Cha u experiments that includ ed trapping intermediate meta l l a cycl es (all of which were four membered) and isotopic labeling Grubbs and Tebbe confirmed that four membered me ta l l a cy c l e rings were indeed an intermediate of the reaction 9 10 Two well studied olefin metathesis reactions at the time were r ing opening metathesis polymerization (ROMP) and homocoupling of propene to yi eld ethene and 2 butene For ring opening reactions, such as the polymerization of cyclopentene 6 the main driving force is thought

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3 to be enthalpic ( H is negative) from the release of energy caused by a red uction of ring strain. M etathesis reactions in general are entropically driven ( S is positive) based on the evolution of ethene gas 4 To date many types of olefin metathesis reactions have been dev eloped, such as asymmetric ring closing metathesis (ARCM), asymmetric ring rearran gements (ARR), asymmetric cross metathesis (ACM), ring closing metath esis (RCM), and asymmetric ring openi ng/cross metathesis (AROCM, Figure 1 b ), the last of which is the focus of this paper. Many catalysts have been developed over the years to facilitate each of these reactions, enabling targeted synthesis. Earlier catalysts required the use of organoaluminum complexes as a cocatalyst for two reasons : f irst they act as a Lewis acid and second they contain organic functionality which transfers a carbene ligand to the TM center The TM center of the catalyst exchange s ligands and/ or form s bridges with the organoaluminum complex facilitating the metathesis reaction olefin metathesis was confirmed, allowing chemists to further develop the methods and catalysts for this reaction One of the fi rst successful olefin metathesis catalysts was developed by Casey and Burkhardt 11 who developed a stable tungsten carbene complex. From earlier observations they found that electron donating heteroato ms bound directly to the carbene carbon stabilize d the complex preventing the TM complex from donating methyl ene to induced an olefin metathesis reaction and help ed chemists such as Schrock and Grubbs undertook the endeavor of synthesiz ing their own catalysts for olefin metathesis reactions.

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4 The nature of bonding in olefin metathesis reactions is well understood. The incoming olefin forms a complex with the metal center, which begins to lengthen the C=C bond. The lengthening is caused by the occupied d orbital on Ru donating its electrons into the vacant molecular orbital on the olefin. This reduces the bond order of the alkene and causes a hybridization change on the carbons from sp 2 to sp 3 Substituents on the carbon atoms then bend away from the center of the forming metallacyclobutane ring because of the hybridization change The coordinated olefin continues to approach until it reaches a transition state (TS ), which is commonly known as cycloaddition. This simultaneousl y lengthens the TM carbene bond and leads to the formation of the intermediate metallacyclobutane Cleavage of the new olefin occurs through another TS, commonly known as cycloreversion. From t his a nother complex is formed with the newly formed olefin, changing the hybridization of the carbons from sp 3 to sp 2 The newly formed olefin has exchanged substituents with the carbene complex and the metathesis cycle repeats C atalyst Schrock et al. developed an octahedral tantalum (and niobium) catalyst (Ta(CH 2 CHMe 3 )(PR 3 ) 2 X 3 where X = Cl or Br) This catalyst resulted in the met athesis of three olefin species: ethylene, propylene and styrene. 12 Adding a carbene ligand to the TM center allowed for the removal of the organoaluminum cocatalyst from the system The need for a Lewis acid still remained however Replacement of two halide ligands with t butoxide resulted i n t he loss of one phosphine ligand, giving a five coordinate species This new catalyst catalyzed the metathesis reaction of cis 2 pentene an internal

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5 olefin The metathesis of cis 2 pentene indicated that coordination could not occur while both phosphine groups were present and an open coordination site was needed. Also i n that work, Schrock expanded to a n octahedral tungsten (VI) based catalyst It was isoelectronic with Ta and Nb based catalysts and contained a similar ligand field The W based catalyst catalyzed terminal olefins at a slow rate. T he addition of AlCl 3 was needed to activate the catalyst giving further evidence for the role of a Lewis acid 12 This work led to a greater understa nding of the TM catalyzed olefin metathesis reaction role as a n alkylidene donor and Lewis acid had been elucidated. Bonding a lkylidene groups direc tly to the TM center eliminated organoaluminum as a cocatalyst The use of a Lewis acid showed the need for weakly bound ligand s that dissociated easily (e.g. phosphine groups ) After dissociation, t he resulting trigonal bipyramidal (tbp) intermediate has an open coordination site which the incoming olefin utilizes during the reaction 13 Tungsten based catalysts developed by Schrock et al. with the formula W(CH t Bu)( N 2,6 C 6 H 3 i Pr 2 )[OCMe(CF 3 ) 2 ] 2 (Figure 2a), were well defined and structurally characterized by X ray single crystal diffraction analysis Schrock et al. also synthesized a Mo based catalyst (Figure 2b, analogous to the highly active W based catalyst) which catalyzed the metathesis of cis 2 pentene at a rate of 250 turnovers/minute, an order of ma gnitude slower than the tungsten catalyst. This is now one of the complexes common ly known as the Schrock catalyst. 14 The catalysts developed by Schrock et al. were highly active and therefor e had limi ted functional group tolerance, low recyclability, and low stability towards air and moisture. This is where Grubbs type catalyst made the greatest strides in the last two decades.

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6 Figure 2. a) Drawing of intermediate metallacyclobutane from first well d efined, highly active, neutral tungsten based catalyst 15 based catalyst 1.4 Grubbs C atalyst Robert Grubbs early work on olefin metathesis entailed examining titanium based catalysts and trying to isolate the resulting intermediate metallacyclobutane In 1980 Grubbs et al. investigated metathesis reactions through the use of unsymmetrical analog s of 10 ( bis ( 5 Cp)TiCH 2 AlClMe 2 ) that catalyzed a slow olefin metathesis reaction. Prior to this, Tebbe and Pars hall tested this reagent in order to determine if it catalyzed olefin metathesis. T hey used isotopically labeled isobutene and methylenecyclohexane as substrates in a degenerate olefin metathesis reaction They observed the exchange of the isotopically l abeled terminal methylene groups con firming its activity in olefin metathesis. 16 Grubbs et al. us ed with terminal alkenes and a Lewis base to isolate metallacyclobutanes which were then characterized by 1 H NMR and 13 C NMR. The isolated metallacyclobutanes were then further reacted with alkenes, alkynes, organoaluminum and H + to observe the resulting products and structures. Indeed, they

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7 observed metathesis products as well as more metallacyclobutane intermediates (Te reagent was reg enerated from the addition of organoaluminum ). This helped verify the existence of the metallacyclobutane as a plausible intermediate in olefin metathesis reactions while also ruling out previously proposed mechanisms The reaction of the metalla cycle intermediate with organoaluminum also display ed the need for the Lewis acid base reaction as part of the metathesis reaction. The Lewis acid facilitates the releas e of the olefin product, while the Lewis base removes the acid from the met al center allowing for subsequent attack of the incoming olefin. 10 Grubbs et al. continued to study Ti based metallacyclobutane complexes through kinetic isotope effects, steric effects on the ring position, and equilibrium constants between the metallacyclobutanes and titanium organoaluminum adducts. 17 18 A key finding from these studies was the cleavage of the carbene carbon from the metal center is a turnover limiting step during the reaction of these metallacyclobutane rings Grubbs e t al. began to turn the focus from early TM complexes for olefin metathesis to late TM complexes. olefin metathesis catalyzed by early TM catalysts had been elucidated However t here were still many draw bac ks from the use of early TM catalysts, such as lim ited functional group tolerance choice of solvents (exclusively organic) and low stability of the catalyst to air and moisture resulting in a low recyclability Grubbs et al. began to study Group 8B meta ls such as RuCl 3 and OsCl 3 in dry organic solvents to facilitate the ROMP of 7 oxanorbornene Group 8B metals were able to produce the highest yields with high molecular polymer weights. 19 20 They next ran the reaction in an emulsion of water and organic solvents. Initial results showed that a long initiation time, sometimes up to 8 days, was required,

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8 limiting the use as a synthetic tool for industry. Further investigation found that the reaction initiated faster in an aqueous solution, and resulted in a rapid ROMP reaction of norbornene derivatives. 21 This study also showed that the solution containing the catalyst after a round of ROMP actually became more active, decreasing initiation times to 10 12 seconds These solutions were reused 14 times, thus alleviating the recyclability problem of early TM catalysts. T he a ctive catalyst was a Ru(II) metal center with a carbene olefin monomer unit formed in situ during the initial ROMP reaction. This ruthenium carbene complex was needed for subsequent metathesis reactions. It is also noteworthy that this experiment successfu lly catalyzed 2 norborne ne 5 methanol, and show ed a growing tolerance for organic functional groups. Following these successful reactions in 1992 Grubbs et al. published a paper detailing the first well defined Ru(II) catalyst which would lead to the Grubbs first generation catalyst. First genera tion Grubbs type catalysts are marked by dihalide and diphosphine ligands bound to a Ru carbene center. The synthesis began with the reaction of RuCl 2 (PPh 3 ) 4 with 3,3 diphenylcyclopropene in a mixture of CH 2 Cl 2 and C 6 H 6 yielding a tbp Ru vinyl carbene species which was confirm ed by X ray diffraction (Figure 3 Precursor to Grubbs I ). This catalyst displayed a marked improvement on the W and Mo based catalysts of its time The solid state catalyst is st able in an inert atmosphere and for several minutes in air It also shows a functional group tolerance by being stable for several days in CH 2 Cl 2 /C 6 H 6 solutio ns containing water or alcohols. 22 It forms block copolymers through the ROMP of 2,3 dideuterionorbornene and perprotionorbornene. This further validated a metallacarbene as an intermediate in the mechanism for olefin metathesis Further experiments confirmed what had already been

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9 observed many times M et athesis reaction s were fairly limited, m ainly to ROMP of strained cyclo olefins such as norbornene. The strained energies of the norbornene systems are calculated to be approximately 10 15 kcal/mol. 23 The driving force of ROMP and the irreversibility of the reaction are primarily from the release of energy caused by a reduction of ring strain, which is presented in the study herein. Figure 3. Generations of well defin ed Ru based Grubbs type catalysts with Grubbs I/II and Grubbs Hoveyda all being commercially available, where Ph = phenyl and Mes = 2,4,6 trimethylphenyl. Grubbs et al. studied the new catalyst ( Precursor to Grubbs I ) by r eact ing it with acyclic olefins that were bound to strained ring systems (methylenecyclopropane and methylenecyclobutane) to see if ROMP would occur. They observed the displacement of the carbene ligand by the cyclomethylene groups, but no further metathesis. Th i s intermediate was then treated with n orbornene and ROMP would occur, confirming that the olefin system needed to be strained. 24 S ince Ru(II) was rich in d electrons, electr on withdrawing ligands mad e t he catalyst more active in a Lewis acid base fashion. The electron withdrawing ligands acidified the Ru carbene bond making it more likely to be attacked by the electron rich olefin bond 24 This information allowed them to tailor their catalyst design. The goal was to allow for selective transformations wh ile decreasing initiation times, increasing the turnover rate all while maintaining catalyst stability

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10 What is now called the Grubbs first g eneration catalyst (Figure 3 Grubbs I ), first generation because it was the first to become commercially available, 25 was synthesized in 1995. 26 27 This new catalyst was a marked improvement on the vinyl carbene analogue improvement over Precursor to Grubbs I Grubbs I displayed a greater synthetic utility than its precursor by conducting ROMP on unstrained cyclo olefins such as cyclooctene. It did, however, produce a broader range of polymer weights and cyclic oligomers due to the increased activity of the cat alyst and back biting. They also explored substituting the para position on the benzylidene ligand, and noted a decrease in the reaction kinetics if the aromatic system was disrupted. 27 Lastly, this new catalyst displayed the ability to metathesize olefins containing functional groups, such as alcohols, allyl chlorides, and allyl acetate s The added functionality can be used to tailor the ROMP product terminal chain for further transformations These catalysts were still limited to mainly conducting ROMP instead of other olefin metathesis reactions. In 19 99 the second generation Grubbs type catalyst (Figure 3 Grubbs II ) was synthesized. The aim was to create a Ru based cat alyst that was more reactive tha n Grubbs I but also maintained its stability to air and moisture. Replacing a phosphine ligand with a n N heterocyclic carbene (NHC) ligand with bulky phenyl groups increased the catalyst activity while maintaining its stability. 28 30 Grubbs II not only conducted ROMP 31 but also catalyz ed ring closing metathesis (RCM) efficiently as or better than the Mo based catalysts of Schrock et al. This added activation stems from enhancing the metal center with the system on the NHC ligand aiding in back bonding It was able to conduct RCM to form di tri and tetra substituted rings that possessed functional

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11 groups such as esters, ethers, and alcohols. It had similar stability compared to the previous generations towards air and moisture, as well as a long stability in organic solvents. All of these factor s are a marked improvement over the early TM catalysts. While the development of Grubbs II was underway, other groups were also trying to improve on Grubbs I 1.5 Grubbs Hoveyda C atalyst Hoveyda, who worked with Schrock on Mo based catalysts, was conductin g ROMP reactions when his group made a discovery in 1999 T he reaction with Grubbs I was essentially non existent when styren e molecules with an ortho substituted methoxy group were present in solution. 32 They reasoned the styrenyl molecule was acting as a chelating agent, bonding to the Ru center through the terminal carbon on the alkene (carbene carbon) and the ortho oxygen atom. They indeed synthesize d and isolate d this ruthenium complex with a chela ting styrenyl ligand, and characterized it by X ray diffraction They then tried this new catalyst in RCM reactions which subsequently failed. They continued to fine tune the chelating group by replacing a methoxy group with the isopropoxy group ( i Pr) (Fi gure 3 Grubbs Hoveyda ) The larger size of the i Pr group compared to the methoxy group aided in the dissociation of the chelate ligand They also reasoned that increased stability may be due to the increased bulkiness of the i Pr group in protecting the Ru center. 32 They further investigated the catalytic activity of their new catalyst in RCM reactions. The catalyst conducted RCM efficiently and was also able to be recovered and reused (at least three additional times) through the use of silica gel column chromatography. The high yield in catalyst recovery also reflects the stability of the complex. This 2 isopropoxy styrene ligand is sometimes referred to as the

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12 Hoveyda ligand. Hoveyda et al. later set out to increase the activity of the catalyst even further, and referred to studies published by many groups including the Grubbs group, which is discussed above. They a lso replaced a phosphine ligand with an NHC ligand and found that synthesis of what is now referred to as the Grubbs Hovey d a catalyst could be carried out from either Grubbs I or Grubbs II 33 Further testing o f the Grubbs Hoveyda catalyst by other groups showed its versatility in many metathesis reactions, such as CM and RCM 33 34 Howev er there were still synthetically challenging points such as stereo and enantioselective reactions Metathesis reactions are equilibrium processes yielding the more thermodynamically stable product in higher yields. With respect to C=C bonds, the more the rmodynamically stable product is the trans isomer. This reduces steric interactions by placing bulky substituents on opposite sides of the C=C bond. Work by Schrock, Hoveyda and co workers showed that Mo and W based catalysts catalyze d Z selective olefin metathesis in the homocoupling of terminal alkenes. 35 36 Ru based catalysts that could affect the same change would also be high ly desirable based on the increased functional group tolerance and stability. 1.6 Stereo and E nantioselective C atalysts Grubbs et al developed such catalysts with chelating NHC ligands that possess a bulky adamantyl chelate, and replac ed the two chloride ligands with a chelating carboxylate ligand (Figure 4 ) 37 The carboxylate ligand can have multiple alkyl groups such as t butyl or methyl (Figure 4 2cat and 3cat respectively) A main difference be tween these catalysts and the previous catalysts (Figure 3 ) is that they are six

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13 coordinate octahedral complexes, instead of five coordinate tbp complexes. However, a Ru(II) center is still believed to be the active catalytic species C atalysts of this type (Figure 4) have displayed high levels of Z selectivity in olefin CM ( up to 95 % Z selective). 37 T he bulky adamantyl chelate (or thiolate ligand) forces olefin attack to one side of the com plex, while the bulky mesitylene group on the NHC ligand forces the substituents on the olefins to the same side of the metallacyclobutane ring. 35 38 39 Other groups had followed the idea of steric hindrance by substituting a chloride ion from Grubbs Hoveyda catalyst with a 2,4,6 triphenyl benzenethiolate ligand (Figure 4 4cat ) which also displayed high Z selectivity in the homocoupling of terminal olefins. 40 Figure 4 Stereoselectiv e derivatives of Grubbs Hoveyda type catalyst with 1cat also being enantioselective in AROCM Computational studies have already been carried out to elucidate the origins of the Z selectivity from 1cat 4cat catalysts and have shown that the side bound mechanism is preferred for 1cat 3cat type catalysts 35 39 41 while the bottom bound mechanism is preferred for the 4cat system 38 Grubbs I / II and Grubbs Hoveyda catalysts. Liu et al. computationally investigated the mechanisms of olefin coordination with 2cat. They utilized the degenerate coupling of ethylene with an active Ru methylidene catalyst coming from 2cat 41 They located eight possible pathways, four bottom bound and four side bound mechanisms. Each of t hese four mechanisms was broken down into one path way that had the carboxylate group in a monodentate configuration while the other

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14 three had it in a bidentate configuration The monodentate metallacyclobutane complexes were lower in energy than the biden tate configuration s but the TSs leading to and fro m the monodentate intermediates were highly disfavored (at least 8.8 kcal/mol) compared to the bidentate complexes. The energetically favored approach of the olefin to the complex was found to be the side bound approach. The Ru methylidene species coded 21 in ref 41 was then utilized in homodimerization calculations to elucidate the origins of Z selectivity. They found that the bottom bound mechanism was disfavored for the coupling of propene, again showing the preference for the side bound mechanism. They locat ed pathways that led to either Z or E butene an d saw that both TSs leading to E butene were disfavore d compared to those leading to Z butene In the E butene pathway, the orientation of the me thyl group towards the mesitylene cap causes steric interactions and increases the energy of the TSs. The study by Liu et al. added insight into the olefi n metathe sis reactions of 1cat 3cat type catalysts, but was not complete A more thorough study by D a ng et al. however, started with the precatalyst 2cat and investigated the homodimerization of 3 phenyl 1 propene. They reasoned that it was unlikely that coordination of the incoming olefin would occur while all six coordination sites were occupied, and th erefore initial dissociation of at least one of the ligands must occur. 35 The initial rupture of the Ru O (isopropoxy) bond via TS1 ( Figure 5) has been shown by computational studies 35 38 39 to be the first step in the formation of the activated catalyst, and is caus ed by the oxygen being a hard donor atom with no negative charge and the Ru(II) center being soft. 35 Once the group has fully rotated and the bottom coordination site is exposed, there is isomerization of the nitrato group to form the tbp intermediate 2 which opens an

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15 equatorial pocket and facilitates the side bound attack of the incoming olefin. 39 Dang et al. considered the binding of the terminal olefin to the open bottom coordination site of complex 1 They locat ed a single pathway which leads to a Ru alkylidene species. This pathway was disfavored however at the cycloreversion TS with a free energy of 42.4 kcal/mol. They then conducted an analysis of the side bound pathways showing that they were energe tically favored. T hey were also able to show the origins of Z selectivity With the side bound attack being favorable, the bulky mesitylene cap forces substit uents on the metallacyclobutane ring to the same side of the ring and results in the Z stereoisomer of the products being formed Dang et al published another paper following this study that utilized 1cat in the same reaction. They received similar result s favoring the side bound mechanism and favoring the Z product. This information along with Liu et al. show the bottom bound pathway to be energetically disfavored and that 1cat 3cat type catalysts proceed through a side bound pathway trans to the adamantyl chelate. 35 39 41 Figure 5. 39 Initiation of precatalyst 3 cat occurs before olefin coordination and is analogous to 1cat / 2cat initiation with solvent corrected free energy and enthalpy (similarly hereafter). Grubbs et al. recently reported the use of enantioenriched 1cat (Figure 4 ), replacing the carboxylate ligand of 2cat / 3cat with a nitrato ligand that catalyzes Z and

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16 enantioselective reactions. They correctly hypothesized the synthesis of enantiopure products from the use of enantioenriched 1cat T he preference for 1cat type catalysts to pr o c e ed through a side bound mechanism trans to the bulky adamantyl chelate and syn to the NHC ligand is the cause of enantiopure products This coupled with the steric bulk from the m esitylene (Mes) cap gives both a Z and enantioselective asymmetric ring opening/cross metathesis (AROCM) reaction. 42 AROCM of norbornene/cyclobutene derivatives with terminal alkenes containing a variety of functional groups produced both Z and enantioselective products ( up to 95% Z 93% ee). 42 Questions regarding the mechanism of the reaction arose though. F or instance why when both Z / E is omers are formed for norbornene derivatives do they have identical % ee, whereas the cyclobutene derivatives do not? Why do norbornenes bearing 7 syn functionality produce more E isomer than Z and w hy do the cyclobutene derivatives produce higher yields than norbornene derivatives? A subsequent Density Functional Theory investigation has been conducted herein, in order to elucidate the origins of both Z and enantioselectivity, as well as answer the questions above. 1.7 Role of Olefin M etathesis The role of olefin metathesis in synthetic chemistry is vast and growing larger every day. It finds great utility in polymer chemistry with the ease of creating block co polymers and being able to control the polymer type based on catalyst functionality. With the greater advent in stereocontrol of the products and more selective CM reactions, it is becoming widely used in targeted organic synthesis. 43 ROMP has also been used to create polymer s with amino acid functional groups that could be subsequently use d in biochemistry. 44 Here in, the AROCM reaction that creates a tri or tetra substituted

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17 cyclopentane ring with up t o four stereocenters and a range of organic functional groups is investigated. These products could be used as possible syn thetic building blocks for anti viral medication s that contain five membered ring s used to rep resent a ribose ring in DNA. The second reaction investigated creates a diene that contains two st ereocenters, both of which are adjacent to C=C bonds and a range of functional group s such as diols. Both products could be used in subsequent synthetic ste ps and transformations to yield a wide range of chemical species.

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18 CHAPTER II D ENSITY FUNCTIONAL THEORY 2.1 T heory, Functionals, and M odels of D ensity Functional Theory Computational chemistry has become an increasingly used tool in the field of chemistry to aid in the understanding and further development of chemical systems bo It allows for the modeling of synthetically difficult molecules, reactions and systems. A dvances in computing power are making it easier to model larger systems, such as proteins, and obtain more accurate results. It can also be relatively inexpensive compared to purchasing chemicals and disposing of waste It is a valuable tool in collaboration with experimental results. Among t he many methods employed, Density Functional T heory (DFT) has become increasingly popular due to its accuracy vs. computation al cost. DFT calculates the electron density of a chemical system, from which electronic energy and other properties may be derived 45 The success of DFT stems from the electron correlation effects that were built in from the beginning, even if the true functional form is unknown 46 This electron correlation contributes to its accuracy. Kohn and Sham introduced a way to approximate inter electronic interactions, 47 through an iterative approach Many approximations have been used to parameterize the exchange correlation functional and provide different tiers of DFT theory. The first approximation is the lo cal spin density approximation (LSDA), which defines the electron density to be constant throughout all space, and is based on a uniform electr on gas. 46 Further approximations

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19 have been made which utilize the gradient of the electron density and are known as generalized gradient approximation (GGA) M eta GGA functionals incorporate LSDA, GGA as well as the spin kinetic energy density of both up and down spin electrons. Hybrid GGA functionals have been introduced which incorporate the exact exchange correlation from Hartree Fock ( HF ) B3LYP utilizes a linear combination of the LSDA exchange, HF exa ct exchange (determined by the S later determinant of Kohn Sham orbitals), Becke s exchange functional, 48 and the correlation functional proposed by Lee, Yang, and Parr, 49 making it a hybrid GGA. 50 B3LYP has been increasing ly used in computational methods based on its relatively low computational cost and decent agreement with theoretical and experimental values 50 makes the use of the B3LYP functional a logical choice for geometry optimizations and frequency calculations. For more accurate results for single point energy calculations, a higher level of theory is employed such as the M06 (Minnesota 2006) class of functionals. M06 51 is a hybr id meta GGA functional that shows great improvement over the commonly used B3LYP functional, and was designed to improve upon the sh ortcomings of other types of DFT functionals Hybrid meta GGA functionals depend on the same variables as hybrid GGA functio nals with the addition of two variables; up and down spin kinetic energy densities. The M06 suit e of functionals have vary ing percentages of non local HF exchange built in, with M06 having the least, when not considering M06 L which has none. This added l evel of exchange is a marked improvement on other DFT functionals, giving improved thermochemistry for transition metals and being suggested

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20 as the functional to use for bond rearrangements in organic and transition metal compounds. 51 An increase in the percentage of HF exchange better describes main group compounds while a decrease better describes TMs. M06 has found a balance which makes it a logical choice for m odeling organometallic reaction pathways Truhlar et al. performed an in depth study comparing many DFT functionals with wave function theories (WFT). 51 Their aim was to model the olefin metathesis of ethylene with a Grubbs II type catalyst [(PH 3 )(NHC)Cl 2 Ru=CH 2 ] and compare the dissociation energies of the phosphine lig and, energy barriers and intermediate energies with that of a composite function used to represent CCSD(T)/AQZQ level of theory. They found that the commonly used B3 LYP /TZQS functional gave a mean unsigned error (MUE) of 11.04 kcal/mol for the reaction pathway and underestimated the stability of the cis geometry pathway. M06 /TZQS however, performed the best of all DFT functionals tested with a MUE of 1.18 kcal/mol, w hich was comparable to the composite function representing CCSD(T)/ATZQ, having a MUE of 1.14 kcal/mol. The authors also noted that the computational cost o f M06 was much more affordable than CCSD(T) or MP2. 52 Truhlar et al also validated M0 6 and many other DFT functionals with a range of databases (notably DBH76 which consists of 76 diverse barrier heights and TMRE48 containing 48 bond energies and reaction energies for transition metal chemistry), and conc luded that M06 was the preferred functional for organometallic react ions involving TMs 51 The choice of basis sets used to represent the atomic orbitals is another crucial part of the computational mo del. The use of multiple primitive Gaussian fun ctions to represent the Slater Type O rbitals (STOs) has become popular because calculating a

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21 Gaussian function is easier and less expensive forward a way to represent t he number of Gaussian functions used to represent STOs For example, 6 31G represent s six Gaussian functions on the core electrons of an atom while the valence electrons are represented by a split valence, one containing three and one with a single primitive Gaussian function. to represent the STOs. The addition of an implies that a polarization function is added to the valence orbital (for main group elements a d orbital), while a second add s p orbi tals to hydrogens. In addition a + may be added to the basis set to represent the addition of diffuse function s to non hydrogen elements, and a second + add s diffuse functions to hydrogens as well. These basis functions are good in representing main group atoms, but the systems herein contain a TM center (Ru) which is represented by a different basis set to aid in computational efficiency The SDD basis set used herein for the TM center was put forth by Preu et al. Using relativistic and quasirelativist ic ab initio calculations as well as empirical data, they d erived a set of energy adjusted pseudopotentials for calculations of TM elements utilizing the frozen core potential. 53 These pseudopotentials are used to decrease computational cost by eliminating the need to explicitly evaluate each M( Z 28 ) + core electron. Finally, a solvation model is needed to properly model the environment of the catalytic reaction investigated here in. Truhlar et al. developed a universal solvation model, Solvation Model Density (SMD) named for its use of electron density. SMD utilizes the electron density of the solute molecule with a continuum description of the solvent The solvent is modeled as a bulk dielectric with surface tension at the solute

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22 solvent barrier. 54 The model was parameterized with 2821 solvation data points, one of which was tetrahydrofuran (THF), the solvent utilized in the experiment Olefin metathesis reactions and catalysts are finding greater utility with in the chemical community. Truhlar et al. and others have chosen to do extensive work on modeling and compa ring DFT theories to the Grubbs type catalyst in olefin meta thesis reactions 51 55 Catalyzed olefin metathesis is a widely used reaction in the pro duction of many materials and the petroleum industry. Without the use of these catalysts, much harsher conditions woul d have to be utilized. These facile catalysts reduce the amount of byproducts from olefin metathesis reactions by guiding targeted synthesis. For these reasons and mor e, it is worthwhile to elucidate the reaction mechanisms underpinnin g these processes in an effort to further aid in the development of this useful tool. 2.2 Computational M etho ds Geometry optimizations were performed in the gas phase at the B3LYP 49 50 level of theory with a mixed basis set of SDD 53 for Ru and 6 31G( d) for all other atoms. The optimized geometries were then subjected to single point energy calculations using M06 51 level of theory and a mixed basis set of SDD for Ru and 6 311++G(d,p) for all other atoms utilizing SMD 54 in THF (the solvent used in the reaction) as the solvation model The M06 functional has been shown by many studies to give accurate energies for Ru complexes in olefin metathesis 51 55 while the use of combined functionals, such as M06/B3LYP, has demonstrated the capability for producing energy profiles for reactions involving TM systems that are in agreement with experimental results 35 38 39 41 56 59 The structure of 1cat is based off of the ORTEP drawing of an intermediate (coded 3 in r ef

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23 42 a) in the synthesis of the catalyst. All calculatio ns were performed with Gaussian 09 60 All Gibbs free energies and enthalpies are given with respect to 1cat in kcal/mol with no entropic corrections included in any calculations. 61 Key structures that are located throughout this study include, but are not limited to, the [2 + 2] cycloaddition/cycloreversion TSs, metallacyclobutane intermediates, complexes prior to/ after cycloaddition/ cyclo reversion, and carbene intermediates. Many experimental results have shown the exis tence of metallacyclobutanes as key intermediates and the [2 + 2] TSs are the ac cepted mechanisms leading to and from them. 9 10 16 All TSs have a single imaginary fre quency that has been visualized and display s the correct atomic motion for a given process. For instance, the cycloaddition/ cyclo revers ion TSs display the increase/ decrease of the C=C/M=C bond distance, while the substituents fold out of/into the C=C/M=C plane, respectively, representing a change in hybridization of the carbon centers from sp 2 to sp 3 or vice versa. All metallacyclobutane bond distances are verified and are in good agreement with expected values ranging from 1.98 to 2.04 for M C bonds and 1.55 to 1.65 for C C bonds. Some comple xes and TSs could not be located. Steric interactions are usually responsible for complexes not being located because of bulky substituents oriented toward the mesitylene cap of 1cat In cases where complexes cannot be located, olefin coordination/diss ociation can be viewed as happening simultaneously with the [2 + 2] cycloaddition/cycloreversion steps, and may not be located as minima on the potential energy surface at the level of theory employed. In fact few complexes leading to/from cycloaddition /cycloreversion were located when the orientation of the terminal olefin

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24 substrate places its substituent near the mesitylene cap (mostly E isomer pathways) which has been observed in other computa tional studies involving Grubbs type catalysts. 35 39 To explain the product ratios, both Z /E and % enantiomeric excess ( ee ) the Boltzmann equation (1) is used (1) E 1 and E 2 represent the free energies of two complexes (TSs), R is the gas constant, and T is the temperature in Kelvin ( 298 .15 K) Using the free energy of the turnover limiting steps in each catalytic cycle, a ratio of products is determined based on kinetics These results are than compared to experimental results in order to elucidate the correct mechanistic pathway. It is important to note that these results are considered to be qualit ative more than quantitative and show a general trend of the reaction mechanism in favoring the formation of certain products over others. 2.3 The Systems Under I nvestigation One norbornene substrate (bicyclo[2.2.1]hept 4 ene, endo 2 ,3 dibenzyloxy, Scheme 1a, coded 9a in ref 42 b) was truncated, replacing the benzyloxy groups with methyl groups. This simplification removes 22 atoms from the system and reduces the computational cost. It is believed that the methyl groups still provide an accurate representation of the steric hindrance imparted by the ether linked benzene groups. The rest of the norbornene derivative system s are without any simplifications, 1cat the

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25 terminal olefin 2 propen 1 yl ester acetic acid, and bicyclo[2.2.1] hept 2 ene,(7 anti ) [4 (trifluoromethyl) phenoxy] ( Scheme 1b coded 9c in r ef 42 b ). Scheme 1 Olefin Metathesis R eactions of N orbornene D erivatives with A llyl Acetate where R exp = O B n and R comp = CH 3 % ee is for B oth S tereoisomers in (b) The cyclobutene derivative system is without any simplification 1cat the terminal olefin 2 propen 1 yl ester acetic acid and the cyclo olefin (1 S, 2 R ) 1,2 di benzyloxy 3 cyclobutene (Scheme 2 ) Scheme 2 Olefin Metathesis Rea c tion of S ubstituted C yclobutene with a Terminal A lkene

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26 CHAPTER III CROSS METATHESIS OF NORBORNENE DERIVATIVES WITH ALLYL ACET ATE SUBSTRATE 3.1 Initiation with 2 Propen 1 yl Ester Acetic Acid (Allyl Acetate) T o Y ield Z and E Active C atalytic S pecies 7 and 4E Starting with intermediate 2 there are four possible orientations the terminal olefin, 2 propen 1 yl ester acetic acid (allyl acetate hereafter), can take, two of which place the acetate group near the Hoveyda ligand, and two with the acetate group away from the ligand. The norbornene derivative, a bulky substrate, was not considered as a probable substrate to initiate the pre catalyst and enter the catalytic cycle. It would have increased steric interactions between itself and the Hoveyda ligand for the initial metathesis reaction com pared to the allyl acetate substrate The proposed active catalytic species by the authors of the experimentally performed paper was a Ru methylidene complex ( 21 ). 21 could be formed by o rienting the acetate group (R1) with t he Hoveyda ligand during cyclo addition (Path I9 I13 Appendix A Scheme A1 and A2 ) These paths have high energy cycloreversion TSs, however, with free energies of 33.4 and 29.6 kcal/mol for TS31 and TS33 respectively, making them disfavored. This type of initiation has also been show n to be disfavored by previous studies because of steric interactions between allyl functional groups (R1) and the Hoveyda ligand (R2) 35 38 A six coordinate octahedral complex ( 3 ) was located by o rienting the allyl acetate away from the Hoveyda liga nd and mesitylene cap (Path I1, Scheme 3). The

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27 equatorial oxygen bond distance increases from 2.19 in 2 to 2.30 in 3 while the axial oxygen bond distance decreases by 0.2 to 2.28 . The formation of the metallacyclobutane ( 4 ) via the [2 + 2] cycloaddition of TS3 is facile with a small free energy of activation (1.3 kcal/mol). The equatorial oxygen bond continues to lengthen in TS3 to 2.36 while axial oxygen decreases to 2.23 This is the case for all of the steps leading to or including the cycloaddition of an incoming olefin. The equatorial Ru O bond is lengthened from an average of 2.17 in the intermediates between each phase (initia tion, coupling, release/regeneration) to 2.29 or greater during the coordination/cycloaddition steps. This coordination helps stabilize the TSs relative to the dissociative cycloaddition TSs that were disfavored or unable to be locate d at the level of th eory employed (Appendix A, Scheme A3) Scheme 3. Possible Pathways for Reaction of Complex 2 with Allyl Acetate Oriented Away from the Mesitylene Cap Leading to Complex 7

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28 The increase in energy caused by dissociation of o ne nitrato oxygen during cycloaddition can be seen by TS7 a dissociative cycloaddition step ( Path I4 Appendix A, Scheme A3 ) which is 8.1 kcal/mol higher in energy than TS3 Complete dissociation of the equatorial oxygen bond occurs upon forming the five coordinate tbp metallacyclobutane ( 4 ). All of the metallacyclobutanes in this study are five coordinate tbp complexes. Complex 4 cycloreverts via TS4 the turnover limiting step having a value of 23.6 kcal/mol A five coordinate complex ( 5 ) follows which dissociates the Hoveyda ligand (CH 2 =CHR2) and results in the active catalytic species 7 ; the Z active catalytic species that leads to the Z product. Two metallacyclobutane rotational isomers can be formed by rotating the nitrato ligand under the ad amantyl group or metallacyclobutane ring (Path I2 and I3, respectively). Not only are these intermediates higher in energy than complex 4 but there cycloreversion steps would also be higher in energy compared to TS4 Cycloaddition via TS3E is analogous to TS3 except for the orientation of R1 (Path I5 Scheme 4 ). This leads to the metallacyclobutane 3E which isomerizes via the nitrato ligand rotating under the adamantyl chelate group ( TS4E essentially isoelectronic with TS3E ) forming metall acyclobutane This places the nitrato ligand between the metallacyclobutane ring and the adamantyl ligand stabiliz ing TS5E by reforming the Ru O equatorial bond (distance 2.29 ) as the Hoveyda ligand ( CH 2 =CH R2 ) dissociates The added stability and reduced sterics of this nitrato position is evident TS5E is at least 7.7 kcal/mol lower in energy ( TS6E TS5E ) than the other cycloreversion steps (Path I6 and I7) TS5E is the turnover limiting step for the formation of the E active catalytic species wi th a free energy of 24.4 kcal/mol, being = 0.8 kcal/mol higher in energy than

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29 TS4 In fact formation of 7 ( Z active catalyst) is favored at every step compared to 4E ( E active cataly s t). This already shows a kinetic bias for forming the Z product I ncreased steric interactions of R1 and the mesitylene c ap are responsible for the energy difference between the two paths as well as 7 being thermodynamically more stable than 4E by 2.0 kcal/mol. Scheme 4 Pos sible Pathways for Reaction of C omplex 2 with Allyl Acetate Oriented Toward the Mesitylene Cap Leading to Complex 4E 3.2 Coupling of 5,6 exo Dimethylbicyclo[2.2.1]hept 2 ene (Norbornene) with Complexes 7 and 4E The bicyclo su bstrate 5,6 exo dimethylbicyclo [2.2.1]he pt 2 ene (norbornene hereafter), has four possible orientations, two exo and two endo, to either of the two active catalytic species ( 7 and 4E ). The exo approach that orients the bridging carbon of

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30 norbornene toward the mesitylene cap and both endo approac hes were shown to be energetically disfavored ( Appendix A Scheme A 4 ). Cycloaddition for these three orientations have high energies, the lowest of which is the exo approach with a free energy of 32.7 kcal/mol ( TS15 ). The increase d energy of these approaches stems from multiple steric interactions between the methyl groups of norbornene the nitrato and mesitylene group s and the bridging carbon with the mesitylene cap. In cases where these steric interactions were minimal, a high degree of ring def ormation occurred. TS14E shows ring deformation by having a Ru C(68) bond distance of 3.38 , approximately 1 longer than analogous bonds in other cycloaddition steps The authors who performed the experiment believed that the Ru methylidene species ( 21 Appendix A, Scheme A1 and A2 ) was first created followed by the attack of the norbornene substrate using this to explain the identical enantioenrichment seen between both the Z and E isomer produc ts (coded 11c 11d and 11e in r ef 42 b ). In fact, formation of complex 21 is disfavored compared to that of 7 or 4E so it cannot be the active catalytic species. T he ide ntical enantioenrichment of both Z / E products is explained by the norbornene substrate having one energetically favorable approach to either of the active catalysts ( 7 or 4E ) Because of this, the initiation of the catalyst plays a role in initially differentiating between the Z / E products. T he olefin geometry in the product is determined by the allyl acetate approach to 2 and not the norbornene derivative approach to 7 / 4E The norbornene approach determines the enantioenrichment of the products The fact that all of the % ee s could be attributed to an intermediate in th e cataly st synthesis having a 95:5 dr (coded 3 in r ef 42 a).

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31 The exo approach with the bridging carbon away from the mesitylene cap is the energetically favorable approach of the norbornene substrate. Cycloaddition of norbornene with complex 7 via TS8 is the turnover limiting step with a free e nergy of 23.0 kcal/mol (Scheme 5 ). This leads to a metallacyclobutane complex 8 which isomerizes to a nearly isoenergetic metallacyclobutane ( 9 ), havi ng an energy of 11.2 kcal/mol. Cycloreversion via TS10 has a low free energy of activation (3.0 kcal/mol) and lead s to comple x 10 that is essential ly isoenergetic with the two pre ceding metallacyclobutanes (Path C1) Olefin dissociation occurs via TS11 result ing in intermediate 11 which has the Z product bound to the Ru center. The equatorial pocket in complex 11 is blocked by the newly formed double bond This space is required for t he side bound attack of a second olefin, which release s the product and regenerate s the active catalytic spe cies Scheme 5 Favorable Coupling Pathways of Norbornene with Complex 7 Leading to Complex 12 The conformational restrictions imparted by the cyclopentane ring and the carbon carbon double bonds of the Ru bound product only allow for the rotation about two

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32 bonds, both of which lie between the cyclopentane ring and the carbon carbon or ruthenium carbon double bonds. It was reasoned that rotation of the bond between the newly formed olefin and the cyclopentane ring would be the lowest energy path on the potential energy surface Indeed a transit ion state ( TS12 not shown) for rotation of the allyl acetate was located, having 0.6 kcal/mol free energy of activation for the elementary step. This resulted in complex 12 which is thermodynamically more stable than 11 by 4.0 kcal/mol. Complex 8 could al so undergo direct cleavage (Path C2) via TS13 and meet back with Path C1 at 11 but Path C2 is disfavored by 3.9 kcal/mol ( TS13 TS10 ). Coupling of norbornene to 4E (Path C3) is analogous to Path C1 (cycloaddition ( TS9E ), metallacyclobutane ( 5E ), nitrato isomerization ( TS10E ), metallacyclobutane ( 6E ), cycloreversion ( TS11E )) and results in intermediate 7E (Scheme 6 ) The only difference between Paths C1 and C3 is that no complex was located after cycloreversion ( TS11E ) due to increased steric interactions between R1 and the mesitylene cap. Cycloaddition via TS9E is the turnover limiting step for coupling to 4E having a free energy of 23.5 kcal/mol. Each intermediate ( 5E 6E and 7E ) is essentially isoenergetic with va lues of 11.5 and 11.9 kcal/mol similar to the intermediates in Path C1. Complex 7E has a similar problem to complex 11 where the newly formed olefin is blocking the equatorial pocket trans to the adamantyl group Rotation of the analogous bond to TS12 yi elded a transition state ( TS12E not shown) with a free energy of 13. 1 kcal/mol, and leads to intermediate 8E which is more stable than 7E by 3.0 kcal/mol. No cycloreversion step leading from 5E could be located at the level of theory employed.

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33 Scheme 6 Favorable Coupling Pathways of Norbornene with 4E Leading to Complex 8E Both resulting complexes ( 12 and 8E ) are t hermodynamically more stable tha n the preceding active catalytic species ( 7 and 4E ) by at least 6.3 kcal/mol ( 7 12 ). T he reduction of ring strain in the cyclo olefin system, as the negative change in enthalpy value s imply are responsible for this stabilization Complex 8E is thermodynamically more stable than 12 by 0.5 kcal/mol because of the E olefin geometry of the newly formed C=C bond. The turnover limiting steps for Path C1 and Path C3 are that of cycloaddition, and structural analysis has been carried out to elucidate the = 0.5 kcal/mol energy difference favoring TS8 over TS9E ( Figure 6 ). Figure 6. Optimized structures of TS8 and TS9E with carbon atoms that form the metallacyclobutane ring labeled, steric interactions marked by dashed lines with distances given in , and H atoms omitted for clarity except those in question.

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34 An increase in energy can be caused by steric interactions due to overlapping van der Walls (VDW) radii (C = 1.7 , H = 1.2 ). The hydrogens located on the allyl acetate are located near carbon atoms on the norbornene substrate, mesitylene cap, and the carbene carbon of the NHC ligand. TS9E steric interactions at 2.69 2.82, and 2.72 , w hich is less than the sum of th eir VDW radii (2.9 ) Analogous hydrogens on TS8 um of the VDW radii at 2.80 . The hydrogens on the allyl acetate responsible for the increase in energy are in the same position relative to the metal lacyclobutane ring as other sterically hindered hydrogens from previous computational studies. 35 38 39 3.3 Release of Z Norbornene Product and Regeneration of Complexes 7 and 4E Complex 12 has the Z product bound to the Ru center, and requires the metathesis of a second allyl acetate to release the product and regenerate the active catalytic species ( 7 or 4E ). The allyl acetate has four possible orientations anal ogous to Paths I1 I15 (Schemes 3 and 4 and Appendix A Schemes A1 and A 2), only two of which ( analogous to Pa th I1 I8 ) that lead to the products resolved in the experimental paper. Of the eight pathways located, the most favorable ones for releasing the Z product and regenerating complex 7 or 4E are shown in Figure 7.

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35 Figure 7. Energy diagram of the low est energy pathways (Path R1 or Path R5) for releasing the Z product ( CH 2 =CH R3) and regenerating complex 7 or 4E respectively. Full Schemes for Path R1 R4 or Path R5 R8 can be found in Appendix A Scheme A 5 or Scheme A 6 respectively. Path R1 is the lowest energy pathway for releasing the Z product and regenerating complex 7 It has an analogous allyl acetate orientation to Path I1 In Path R1 a TS ( TS17 ) leading to a n essentially isoenergetic complex ( 13 ) was located, w ith free energy values of 15.6 and 15.2 kcal/mol, respectively. Cycloaddition via TS18 leads to the metallacyclobutane complex 14 which has a low point on the potential energy surface of 2.8 kcal/mol. The low energy of 14 causes a large energy of activati on (19.3 kcal/mol) for the elementary step of cycloreversion ( TS19 ). In Path R1, TS19 is the turnover limiting step ( = 22.1 kcal/mol). This increased energy is caused by s teric interactions between the nitrato ligand and many hydrogen s on the cyclopentane product ( CH 2 = CH R3 ), and the allyl acetate bound to the Ru center Cycloreversion leads to a complex ( 15 ) and the product dissociates via TS20 resulting in complex 16 All of the intermediates and TSs between complex 14 and 16 have relatively high points on the

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36 potential energy surface with TS19 being the turnover limiting step ( = 22.1 kcal/mol ) Complex 16 is a tetrahedral intermediate with only four ligands bound to the Ru center, where a Ru O nitrato bond is still broken. To complete t he catalytic cycle, the tbp c omplex 7 was reg enerated by decreasing the Ru O(equatorial) N (nitrato) bond angle via TS24 The increase in the coordination number on the Ru center from the second oxygen makes complex 7 thermodynamically more stable than complex 16 by 1.2 kcal/mol. Path R5 is analogous to Path I5, with the allyl acetate oriente d toward the mesitylene cap, which will release the Z product and regenerate complex 4E (Figure 7 ). Cycloaddition of the allyl acetate to complex 12 occurs via TS25 and results in the metallacyclobutane complex 17 Complex 17 isomerizes via TS26 giving metallacyclobutane which cycloreverts via TS27 releasing the Z product ( CH 2 =CH R3) and regenerating complex 4E The Ru O equatorial bond is reforming in TS27 with a distance of 2.29 , stabiliz ing the complex as the product dissociates 3.4 Release of E Norbornene Product and Regeneration of Complexes 7 and 4E Of the possible pathways located (Path R9 R16) for releasing the E product and regenerating the active catalytic species, Figure 8 shows the two most favorable leading to 7 or 4E respectively. The release of the E product and regeneration of complex 4E (Path R13) is analogous to Path R5 and Path I5. Coordination and cyc loaddition occur simultaneously via TS24E with a high free energy of 25.5 kcal/mol, making it the turnover lim iting step in Path R13 (Figure 8 ). The metallacyclobutane complex 11E isomerizes via TS25E to a nearly isoenergetic metallacyclobutane Clea vage of

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37 c omplex via the high energy TS26E ( = 25.1 kcal/mol) dissociates the E product ( CH 2 =CH R4), resulting in the E active catalytic species ( 4E ). The nitrato ligand is again oriented so the Ru O equatorial bond can reform as the product dissocia tes, and has a distance of 2.29 in TS26E the same as TS27 Figure 8. Energy diagram for the lowest energy pathways (Path R9 and R13) for releasing the E product ( CH 2 =CH R4) and regenerating complex 7 or 4E respectively. Full Schemes for Path R9 R12 or Path R13 R16 can be found in Appendix A Scheme A 7 or Scheme A 8 respectively. The E product can be released while also regenerating the Z active catalytic species 7 through Paths R9 R12, which are analogous to Path R1 R4. Transition state TS17E leads to complex 9E which cycloadds via TS18E and leads to metallacyclobutane 10E Metallacyclobutane 10E isomerizes by rotating the nitrato ligand under the metallacyclobutane ( TS19E ), and forms metallacyclobutane 1 having the nitrato ligand directly below the metallacyclobutane ring. Cycloreversion via TS20E is the turnover limiting step for releasing the E product and regenerating the Z active catalytic species ( 7 ) with a free energy of 19.2 kcal/mol. This is isoenergetic with

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38 TS27 the turnover limiting step in Path R5. It can be seen from Figure 8 that formation of complex 7 from 8E is favored at every step in comparison to reforming 4E 3.5 Coupling of B icyclo[2.2.1] hept 2 ene, (7 anti ) [4 (trifluoromet hyl) phenoxy] ( N orbornene*) with C omplex 7 and 4E To further validate the proposed mechanism for AROCM of norbornene derivatives, a second bicyclo derivative, bicyclo[2.2.1] hept 2 ene,(7 anti ) [4 (trifluoromethyl) phenoxy] ( coded 9c in r ef 42 b and norbornene hereafter), was investigated. For clarity purposes and since most of the complexes and pathways are analogous to the norbornene substrate, all complexes and products will be marked w ith a *, to de note the use of norbornene* as the substrate. Similar to coupling of norbornene, the enantioselectivity for this reaction is caused by both endo approaches and one exo approach of norbornene* being energetically disfavored. Of these approache s the lowest energy TS analogous to TS15 has a free energy of 33.0 kcal/mol ( TS17* Appendix A Scheme A 9 ). The norbornene* substrate has an ether linked trifluoromethyl phenyl group (R5) bound to the bridging carbon whose orientation has a large effect o n the free energy of the system. Therefore, there are two cycloaddition complexes, for each active catalyst, that use the exo face of the system with the bridging carbon pointed away from the mesitylene cap. These complexes differ in their orientation of R5. Placing R5 near R1 increases steric interactions ( A ppendix A Figure A 1) during the coupling process to complex 7 and 4E This increases the energy of the cycloaddition steps TS15* and TS15E* ( A ppendix A Scheme A 9 ) having free energies of 25.7 and 24.6 kcal/mol, respectively.

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39 Placing R5 near the nitrato ligand while utilizing the exo face of the system is the most favorable approach for norbornene* to either complex 7 or 4E Coupling of norbornene* to complex 7 (Paths C1* and C2*) is analogous to the coupling of norbornene (Paths C1 and C2), where the cycloaddition step ( TS8* ) is the turnover limiting step with a value of 22.5 kcal/mol (Scheme 7 ) This is 3.2 kcal/mol lower in energy than TS15* Following Path C1 *, a metallacyclobutane is formed which isomerizes via the nitrato ligand rotating under the adamantyl chelate and results in metallacyclobutane complex 9* Cycloreversion via TS10* leads to a complex which dissociates the newly formed olefin ( TS11* ) and results in intermediate 11* Scheme 7 Coupling of Norbornene* with C omplex 7 Coupling of norbornene* to complex 4E (Paths C3* and C4*) is analogous to the coupling of norbornene (Path C3 and C4) C ycloaddition ( TS9E* ) is the turnover limiting step with a free e nergy of 24.2 kcal/mol (Scheme 8 ), and is 0.4 kcal/mol lower in

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40 energy than TS15E* From cycloaddition, metallacyclobutane 5E* is formed which isomerizes by rotati ng the nitrato ligand via TS10E* and results in me tallacyclobutane 6E* The newly formed olefin moves away via TS11E* and results in intermediate 7E* Nitrato isomerization in Paths C1* and C3* again allow for coordination of the equatorial oxygen bond as cleavage of the olefin occurs, stabilizing the TSs Scheme 8 Coupling of Norbornene* with C omplex 4E Complex 11* and 7E* have the newly formed olefin blocking the equatorial pocket, analogous to complexes 11 and 7E R otation of the olefin occurs via TS12* and TS12E* (analogous to TS12 and TS12E ) and results in complexes 12* and 8E* respectively. To facilitate the release of the product and regeneration of the active catalytic species, R5 was rotated away from the bulk of the catalysts, and placed on the same side of the cyclopentane ring as the newly formed olefin. TS13* could not be located due to steric interactions between R1 ( Z isomer ) and R5. TS13E* (not shown) was located, however, with a 0.9 kcal/mol free energy of activation for the elementary

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41 step. The resu lting intermediates ( 13* and 9E* ) are thermodynamically more stable than the preceding intermediates ( 12* and 8E* ) by 2.8 and 2.1 kcal/mol, respectively. Structural analysis of the turnover limiting steps located steric interactions that explain the higher energy of TS9E* over TS8* favoring the formation of the Z product Hydrogens on the allyl acetate group in TS8* and TS9E* (analogous to hydrogens on TS8 and TS9E respectively ) are responsible for the increase in energy (Figure 9 ). TS8* has three steric interactions where the distance between the atoms is less than the sum of their VDW radii, where TS9E* displays six of these interactions. It is important to note that TS15* and TS15E* have similar steric interactions as the ones shown in Figure 9, but al so contain additional interactions which are shown in Appendix A Figure A1. Figure 9 Optimized structures of TS8* and TS9E* with steric interactions marked by dashed lines with distances given in , and H atoms omitted for clarity except those in question. VDW ra dius of oxygen is 1.52 . Analogous high energy structures ( TS15* and TS15E* ) where the R5 orientation is changed ar e located in Appendix A Figure A 1.

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42 3.6 Release of Z N orbornene Product and R egeneration of Complexes 7 and 4E A second allyl acetate approaches complex 13* with R1 oriented either away from or towards the mesitylene cap ( TS20* or TS22* ) and result s in m etallacyclobutanes 14* or 15* respectively (Figure 10 ). From complex 14* cycloreversion occurs via TS21* with a free energy of 20.1 kcal/mol, and results in the Z product being released while regenerat ing the Z active catalyst From metallacyclobutane 15* isomerization of the nitrato ligand occurs via TS23* and results in metallacyclobutane complex 16* Cleavage occurs releasing the Z product via TS24* ( = 19.6 kcal/mol ) and results in the E active catalytic species. The turnover limiting steps for the release of the Z product in Path R1 or R2 is that of cycloreversion ( TS21* / TS24* ). F ormation of the E active catalytic species is favored by 0.5 kcal/mol ( TS21* TS24* ) when releasing the Z product* similar to the release of the Z product Figure 10 Energy diagram for the lowest energy pathways (Path R1* and R2*) for releasing the Z product (CH 2 =CH R6) and regenerating complex 7 or 4E respectively. A complete scheme for the release of the Z product and reg eneration of complex 4E can be found in A ppendix A Scheme A 10

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43 3.7 Release of E N orbornene* P roduct and R egeneration of Complexes 7 and 4E Followin g Path R7* (Figure 11 ) the allyl acetate cycloadds to complex 9E* via TS20E* with a free energy of 23.3 kcal/mol and has the incoming R1 group oriented away from the mesitylene cap. This leads to metallacyclobutane 10E* which cycloreverts via TS21E* ( = 22.6 kcal/mol) releasing the E product and regenerating complex 7 The other orientation of the allyl acetate, oriented toward the mesitylene cap (Path R6*), results in the cycloaddition step of TS22E* with a free energy of 22.9 kcal/mol. From TS22E* a metallacyclobutane ( 11E* ) was located which cycloreverts via TS23E* being essentially isoenergetic with TS22E* and releases the E product and regenerates the E active catalytic species ( 4E ). The turnover limiting steps for the release of the E product are that of cycloaddition, although the energies of cycloreversion w ithin the same path ways are less than 0.7 kcal/mol difference ( TS20E* TS21E* ). Figure 11 Energy diagram for the lowest energy pathways (P ath R6* and R7 *) for releasing the E product ( CH 2 = CH R7) and regenerating complex 7 or 4E respectively.

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44 The orientation of R5 during the release and regeneration phase again plays a role in the free energy of the system. A second allyl acetate could complex with 12* or 8E* (Scheme 5 or 6 respectively ), where the R5 group is oriented toward the bulk of the catalyst, but were shown to lead to high energy transition states during the release and regeneration phase. The most favorable path from complex 12* that regenerates complex 7 (Path R8*, Appendix A, Scheme A11) would lead to a high energy cycloreversion transition state ( TS30* ) that is at least 3.6 kcal/mol higher in energy ( TS30* TS21*) th an any transition state in Path R1* or R2*. T he reaction of complex 12* to reform complex 4E has cycloadditio n TSs that are higher in free energy than those in Path R2* ( A ppendix A Scheme A 12 ). Coupling to complex 8E* could lead to a lower energy cycloaddition step ( TS24E* Appendix A Scheme A 1 3 ) but would result in high energy cycloreversion TSs the lowest of which has a free energy of 25.4 kcal/mol ( TS25E* ) T hat is 2.1 kcal/mol higher in energy than any transition state in Paths R6* or R7* and higher in energy than the turnover limiting step in the coupling phase ( TS9E* ) A complete scheme for the high ener gy orientation of R5 that releases E product* and regenerates 4E is l ocated in Appendix A, Scheme A14 3.8 Turnover Limiting S teps in the AROCM of Norbornene D erivatives From initiation through regeneration, the formation of the Z product is favored in every phase of the catalytic cycle. Initiation favors the formation of the Z active catalytic species by differentiating the cycloreversion steps ( TS4 and TS5E ) which have an energy difference of = 0.8 kcal/mol in favor of TS4 This energy difference gives a Z / E product ratio of 4:1 alr eady showing favored kinetics for the formation of the Z products. TS4 and TS5E have different coordination environments where the Ru O (equatorial)

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45 bond is reforming in TS5E having a distance of 2.29 , while in TS4 this bond is completely broken. Due to the different coordination environments, it is difficult to conduct a structural analysis between the two species to elucidate the cause of the energy difference. Initiation can be viewed as a one time process to enter the catalytic cycle as long as the potential energy surface has low enough energy barriers, causing the most substantial differentiation of products to be due to the turnover limiting steps in the coupling or re generation phases of the cycle. Focusing on norbornene, the turnover limiting step (global maximum of the most favorable path way) for the formation of the Z / E product occurs during the cycloaddition steps ( TS8 / TS9E ) of the coupling phase. The difference in energy is = 0.5 kcal/mol, favoring TS8 and giving a Z / E product ratio of 7:3. The highest energy barrier for the regeneration of 7 ( TS19 in Path R1 and TS20E in Path R9) is lower in energy than TS8 by at least 0.9 kcal/mol ( TS8 TS19 ), giving two possible pathways for reforming the Z active catalytic species. The regeneration of 4E only has one favorable pathway (Path R5) with a lower energy barrier than the global turnover limiting step ( TS9E ) which releases the Z product. Path R13, which releas es the E product and regenerates 4E has two high energy barriers for cycloaddition ( TS23E ) and cycloreversion ( TS25E ) with free energy values of 25.5 and 25.1 kcal/mol, respectively. This means there is only one energetically favorable pathway (Path R5) t hat reforms 4E and only one energetically favorable pathway (Path R9) that releases the E product further hindering the formation of the E product The difference in energy between the turnover limiting steps in Path R5 (release Z product and regenerate 7 ) and Path R13 (release E product and regenerate 4E ) is 3.4

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46 kcal/mol ( TS24E TS19 ) in favor of TS19 ( Path R5). Since there are two energetically favorable pathways to regenerate complex 7 (Path R1 and Path R9) but only one to rege nerate complex 4E ( P ath R5 ), a decrease in the concentration of 4E relative to 7 will occur as the catalytic cycle progresses. This will result in a higher probability of complex 7 coupling with the norbornene substrate, increasing the Z / E product ratio fr om 7:3 closer to the experimental value of 95:5 Z / E 42 It is unique that the favorable reformation of the active catalytic species stems from the release of the opposite product (releasing Z product regenerates 4E and releasing E product regenerates 7 ), which has not been observed in other olefin metathesis computational studies to date. Focusing on norbornene*, the difference in energy between the global turnover limiting steps is 1.7 kcal/ mol ( TS9E* TS8* ) which gives a Z / E ratio of 18:1, where the experimentally performed paper displayed a Z / E ratio of 7:3. 42 During the release and regeneration phase however, the formation of the E ac tive catalytic species ( 4E ) is favorable compared to that of complex 7 Releasing the Z or E product favorably regenerates 4E by 0.5 or 0.4 kcal/mol ( TS21* TS24* or TS20E TS22E* respectively ). As the catalytic cycle repeats, the concentration of 4 E would increase, allowing for more E product to form and skew the 17:1 Z / E ratio closer to the experimental value of 7:3. The release of the E product must overcome higher energy barriers compared to releasing the Z product *. Since complex 4E is favorabl y regenerated, this creates a bottle neck in releasing the E product*, slow ing the reaction as the c ycle repeats. This offers insight into norbornene* producing the lowest yield (40%) 42 of any of the norbornene derivatives tested.

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47 The energy difference between TS8 and TS15 ( = 9.7 kcal/mol) favors TS8 and gives a calculated % ee of 100 qualitatively agreeing with the experimentally observed 93% ee. This can be adjusted based on the fact that an experimental intermediate in the synthesis of 1cat had a dr of 95:5 and would lower the calculated % ee closer to the experimental value the degree of which cannot be accurately determined 42 Hypotheses based on the approac h of the norbornene derivatives explain the Z / E ratio and enantioselectivity of other substrates tested in r ef 42 The favorable exo approach in Path C1, C5, C1*, and C3* would place the syn ether linked benzene in the norb ornene derivative (coded 9d in r ef 42 b and is the only substrate that favors the formation o f the E isomer) directly in the space that the nitrato ligand occupies. It is hypothesized that for this species the endo approach with C(5) and C(6) of the bicyclo system oriented towards the mesitylene cap (analogous to TS14 and TS14E A ppendix A Scheme A 4 and TS18* TS19* TS18E* and TS19E* A ppendix A Scheme A 9 ) would be most favorable, allowing the ether linked benzene ring to be oriented away from the mesitylene cap and the bulk of the catalyst. This approach to complex 7 would actually yield the E isomer instead of the Z isomer product while the same approach to complex 4E would yield the Z isomer This explains the preferred formation of the E isomer product w hen utilizing a norbornene derivative with syn functionality This norbornene derivative also has a nearly identical enantioenrichment between Z / E isomers, hypothesized to be caused by the one favorable approach of the norbornene derivative.

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48 CHAPTER IV CROSS METAT HESIS OF CYCLOBUTENE DERIVATIVE AND ALLYL ACETATE 4.1 Coupling of ( S R ) 1,2 D ibenzyloxy 3 cyclobutene to Complex 7 Grubbs et al. also performed the AROCM of cyclobutene derivatives that resulted in similar Z selectivity but higher yields. 42 A notable difference between the two strained cyclo olefin substrates is the lower enantiomeric excess measured for the E isomer products of cyclobutene compared to norbornene For clarity, all of the cyclo butene derivative complexes will be named with C B (standing for CycloButene) including the products. For example the Z product created from cyclobutene will be denoted Z CB product. ( S R ) 1,2 d ibenzyloxy 3 cyclobutene (c yclobutene hereafter) couples to the active catalytic species ( 7 and 4E ) in a si milar fashion as norbornene. Following Path C11 (Scheme 9), cyclobutene approaches complex 7 trans to the adamantyl group with its bulky benzyloxy groups oriented away from the mesitylene cap ( TS8 CB ). The benzyloxy groups are also pointed away from the b u lk of the catalyst and R1. This coordination lengthens the equatorial nitrato bond to 2.31 . T he ring strain of the cyclo butene ring activates the C=C bond, causing the bond distances in the TSs (cycloaddition/cycloreversion) to have values closer to what would be expected for complexes. The emerging Ru C and C C bonds in TS8 CB (marked by a single dashed line in Scheme 9) have distances of 2.32 and 2.44 , respectively. The cyclobutene C=C bond and Ru=C bond (marked by a sol id and dashed line) have distances of 1.39 and 1.87

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49 respectively The release of ring strain causes a large Gibbs energy and enthalpy change ( G = 23 .0 kca l /mol and H = 24.3 kcal/mol) upon forming the metallacyclobutane ( 8 CB ) T he metallacyclobutane ring has bonds that are comparable to others seen throughout this study, even though they are on the outer edge of the mean. Scheme 9. Coupling of Cyclobutene to C omplex 7 Isomerization of the nitrato ligand ( TS9 CB ) yields metallacyclobutane 9 CB which is nearly isoenergeti c with 8 CB Relative to the cycloreversion TSs, isomerization of the nitrato ligand has a high point on the potential energy surface (6.4 kcal/mol) It is still considered facile because of the l arge exothermic/exergonic step of cycloaddition moving to the preceding metallacyclobutane. In this orientation, the nitrato ligand can stabilize the complex as olefin cleavage occurs by reforming its equatorial bond. Cycloreversion ( TS10 CB ) has a free en ergy of 5.2 kcal/mol, but the favorable enthalpic contribution from the release of ring strain is still maintained with a value of 11.2

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50 kcal/mol This cycloreversion TS also has bond distances different from those seen in the norbornene derivatives coupli ng. The Ru C and C C bonds that are breaking (marked by single dashed lines) are 2.15 and 1.83 , respectively. The Ru=C and C=C bond s that are reforming (marked by a dashed and solid line) are 1.92 and 1.47 respectively. The bond lengths in TS8 CB and TS10 CB are representative of the bond d istances observed throughout this study using cyclobutene as a substrate. The change in enthalpy from complex 7 to the intermediate complex 10 CB is 35.4 kcal/ mol The exergonic/exothermic nature of the system cont inues as the newly formed double bond moves away from the bulk of the catalyst This newly formed olefin is blocking the equatorial pocket trans to the adamantyl ligand need ed for subsequent olefin attack and therefore must be rotated out. In order to make enough room for a second allyl acetate t he complex must overcome two TSs ( TS11 CB and TS12 CB ) that are much low er in energy than cycloaddition or cycloreversion. R otation of the bond adjac ent to the newly formed olefin ( CH=CHR1 ) results in a tbp intermediate 12 CB Intermediate 12 CB is 21.8 kcal/mol lower in free energy than the active catalytic species 7 and has the bulky benzyloxy groups oriented away from the bulk of the catalyst There are three other orientations that the cyclobu tene derivative can take to the active catalyti c species, only one of which ( TS14 CB ) was successfully located (Scheme 9) TS14 CB (27.0 kcal/mol) approaches 7 with the benzyloxy groups oriented toward the body of the catalyst and place s the bulky groups n ear the nitrato ligand and R1 (Path C13) The benzyloxy group closest to the nitrato ligand is forced to rotate sideways orienting the plane of the benzene ring perpendicular to the plane of the cyclobutene ring

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51 (Figure 12) A hydrogen on the methylene car bon of the benzyl group is 2.13 away from a hydrogen on the cyclobutene ring bonded to the same parent carbon as the benzyloxy group. A lesser steric interaction exists between these two hydrogens in the free cyclobutene, but the distance is 2.37 . The other hydrogen on the methylene carbon is 2.60 away from a nitrato oxygen (not shown) while the benzyloxy oxygen on the same group is 2.8 1 away from the nitrato nitrogen (VDW radius of N is 1.55 ). These distances are all within the sum of the VD W radii, causing TS14 CB to be 2.8 kcal/mol higher in free energy than TS8 CB although they are isenthalpic The increase in energy causes Path C13 (Scheme 9) to be disfavored. It is important to note that these steric interactions are in addition to the steric interactions that both complex TS14 CB and TS8 CB share, which will be discussed S ection 4.5. Figure 12 Optimized structure of TS14 CB showing steric interactions that differ from TS8 CB marked by dashed lines and all distances given in with hydrogens omitted for clarity except those in question VDW radius of N is 1.55 Two more approaches of cyclobutene to complex 7 are imaginable, both with the benzyloxy groups oriented up toward the mesitylene cap. One ori ents the bulky groups

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52 away from the bulk of the catalyst while the other places the groups in between the Ru=C bond and mesitylene cap of 7 Neither of these complexes was located because of large steric interactions however 4. 2 Coupling of ( S R ) 1,2 D ibenzyloxy 3 cyclobutene to C omplex 4E The cyclobutene substrate also couples to complex 4E in order to produce the E CB product. Cycloaddition ( TS9E CB ) has a high free energy barrier of 26.6 kcal/mol with a 9.3 kcal/mol free energy of activation for the elementary step (Scheme 10) Again the approach places the benzyloxy groups away from the mesitylene cap and the bulk of the catalyst analogous to TS8 CB As the olefin coordina tes, the equatorial nitrato ligand bond distance increases to 2.30 . The resu lting tbp metallacyclobutane (5 E CB ) is 20 .0 kcal/mol lower in free energy than TS9E CB and 10.7 kcal/mol lower than the active catalytic species (26.6 kcal/mol lower in enthalpy). Isomerization of the nitrato ligand could occur, enabling it to stabilize c omplex 6E CB as it cleaves the double bond (TS not located), however TS14E CB (nitrato isomerization) has the second highest energy (10.9 kcal/mol) of all the complexes in Paths C14 C16. Instead, direct cleavage of 5E CB via TS10E CB occurs, shifting the benzyloxy groups away from the nitrato ligand This is a facile step with a small free energy of activation of 2.1 kcal/mol. A complex was located ( 7E CB ) as the nitrato ligand moves the equatorial oxygen under the Ru center with an energy of 0.5 kc al/mol No TS could be located for the isomerization of the nitrato ligand to reform its bidentate chelate, but this is not believed to be a turnover limiting step. An intermediate ( 8E CB ) was located however with the newly formed olefin dissociated and b oth nitrato chelate bonds reformed. 8E CB still has the newly formed olefin blocking the equatorial pocket analogous to 10 CB The complex must

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53 again rotate this group ( CH = CHR1) over two low energy TSs ( TS12E CB and TS13E CB ) resulting in intermediate 10 E CB The highest elementary barrier the complex must overcome for rotation of this group is 5.3 kcal/mol ( 9E CB ) The resulting intermediate ( 10E CB ) is 23.6 kcal/mol lower in free energy than the active catalyst 4E and essentially isoenergeti c with 12 CB Scheme 10 Coupling of Cyclobutene to C omplex 4E Path C16 is another possible approach of the cyclobutene substrate to 4E (analogous to Path C13) and would orient the benzyloxy groups near the nitrato ligand ( TS15E CB Scheme 10 ). The benzyloxy group is again torqued (analogous to TS14 CB ) causing increased steric interactions. In TS15E CB this rotation causes two hydrogen atoms to be 2.10 apart and the benzyloxy oxygen is 2.89 and 2.56 away from ni trogen and a n oxygen in the nitrato ligand respectively (Figure 13 ) The oxygen on the other benzyloxy group is 2.24 away from a hydrogen on the allyl acetate substrate (not shown) TS15E CB has more steric interactions (not shown) that are

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54 analogous to complex TS9E CB which will be discussed in S ection 4.5 These limited approaches that the cyclo olefin substrate can take shed light on the % ee seen in the experimental results. Figure 13 Optimized structur e of TS15E CB showing steric interactions of select atoms marked by a dashed line with all distances given in and h ydrogens omitted for clarity except those in question. 4.3 Release of th e C yclobutene Z CB P roduct and R egeneration of C omplex es 7 and 4E A second allyl acetate is required to release the Z CB product of the cyclo butene reaction and complete the catalytic cycle. There we re seven paths located (Path R17 R23 ) for regenerating the active catalyst and releasing the Z CB product. T he two most fav orable are shown in Figure 14. The allyl acetate coordinates to 12 CB forming a complex ( 14 CB ) with the acetate group oriented away from the mesitylene cap This orientation of R1 regenerates complex 7 The increased steric hindrance caused by R8 (the Ru bound product) causes the nascent nitrato equatorial bond to have a distance of 2.44 . This leads to cycloaddition ( TS15 CB ) which forms a low energy

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55 metallacyclobutane 15 CB ( = 5.8 kcal/mol) Isomerization of the nitrato ligand occurs via TS16 CB and gives a higher energy metallacyclobutane ( CB ) with a free energy of 1.0 kcal/mol. Cleavage of the double bond is the turnover limiting step with a free energy of 13.4 kcal/mol The increased energy is caused by ring pucker T he newly formed doubl e bond is twisted away from the mesitylene cap causing this deformation T his and t he bulkiness of the substituents in R8 has increased steric interactions with the catalyst scaffold and causes a 14.4 kcal/mol energy of activation. 16 CB a complex, is formed which then releases the Z CB product, resulting in complex 7 Figure 14 Energy diagram of the two most favorable pathways releasing the Z CB product and regenerating the active catalytic species 7 or 4E respectively. Complete schemes for the regeneration of complex 7 or 4E are in Appendix A Scheme A15 or A16 respectively. A complex could not b e located in Path R20 due to steric interactions (Figure 14 ). Cycloaddition was located, however, with a larg e free energy of activation for the elementary step of 15.8 kcal/mol caused by steric interactions of R1, the mesitylene cap and R8 A metallacyclobutane ( 17 CB ) follows, leading to cyclorev er sion ( TS20 CB ). TS20 CB has a free energy of 1 0.6 kcal/mol, whi ch is 2.8 kcal/mol lower in free energy

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56 t han the analogous TS in Path R17 ( TS17 CB TS20 CB ). A complex ( 18 CB ) was located with a free energy of 4.0 kcal/mol, which then releases the Z CB product and regenerates 4E The turnover limiting steps for releasing the Z CB product favor formation of complex 4E by 2.8 kcal/mol in the cycloreversion steps Forming 7 is thermodynamically more favorable than 4E by 2.0 kcal/mol because of reduced steric interactions of R1 and th e mesitylene cap 4.4 Release of the C yclobutene E CB P roduct and Regeneration of C omplex es 7 and 4E Six pathways for the release of the E CB product have been located, and the two most favorable pathways regenerating complex 7 or 4E are shown in Figure 15. Regeneration of the active catalytic species 7 from 10E CB (Path R24 ) begins with the cycloaddition of allyl acetate via TS16E CB having a free energy of 6.3 kcal/mol and completely dissociating the equatorial oxygen bond This TS is essentially isoenergetic wit h the analogous TS from Path R17 ( TS15 CB ) This leads to a metallacyclobutane ( 11E CB ) which isomerizes via TS17E CB and results in an isoelectronic metallacyclobutane CB with a free energy of 9.1 kcal/mol. A larg e free energy (16.9 kcal/mol) of activation for the elementary step to reach cycloreversion ( TS18E CB ) is required. The equatorial nitrato bond in TS18E CB is reforming with a distance of 2.32 and stabilizes the complex as it releases the E CB product an d reforms complex 7 All of the metallacyclobutanes in Paths R24 and R25 have low points on the potential energy surface the highest of which ( CB ) has a free energy of 5.9 kcal/mol ( Appendix A Scheme A17 ). Only one cycloreversion step was located fo llowing these

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57 metallacyclobutanes caused by the likely high energy of activations for the elementary steps. F igure 15 Energy diagram for the release of E CB product and regeneration of the active catalytic species 7 or 4E (Path R24 or Path R26 respectively). Full sc hemes are located in A ppendix A Scheme A17 or A18 respectively. Complex 4E is regenerated from 10E CB (Path R26 ) through the cycloaddition of the allyl acetate with R1 oriented toward the mesitylene cap TS19E CB has a large free energy of activation for the elementary step of 18.6 kcal/mol and is the turnover limiting step for the release of the E CB product and regeneration of 4E This leads to a metallacyclobutane 12E CB which cycloreverts via TS20E C B to yield complex 13E CB The nitrato ligand is only bound through a single oxygen after dissociation of the E CB product ( 14E CB ) To complete the catalytic cycle, complex 4E must be regenerated. Complex TS24E CB reduces the bond angle of Ru O( equatorial ) N(nitrato) with a free energy of 4.4 kcal/mol, and regenerates complex 4E The formation of complex 7 is

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58 favored at every step of the regeneration phase that releases E CB product beginning with 10E CB This means that releasing the E product f avorably regenerates complex 7 4.5 Turnover L imiting S teps in the AROCM of C yclobutene The turnover limiting steps for the catalytic cycle of cyclobutene are analogous to norbornene. T he coupling of cyc lo butene to the active catalytic species ( TS8 CB and TS9E CB Scheme 9 and 10, respectively ) has a = 2.4 kcal/mol favoring TS8 CB Using equation (1), this gives a Z / E product ratio of 57 :1 qualitatively agreeing with the experimental value of 85:15 Z / E After the initia l differentiation in initiation favoring the Z over the E active catalytic species there continues to be favorable energetics both kinetically and thermodynamically, for the formation of the Z CB product. Structural analysis (Figure 16 ) of the optimized turnover limiting steps ( T S8 CB and TS9E CB ) has been carried out in order to elucidate the cause of this difference in energy. Figure 16 Optimized structure s of TS8 CB and TS9E CB with steric interactions marked by dashed line s all distances given in , and H atoms omitted for clarity except those in question.

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59 Both emerging metallacyclobutane rings in the cycloaddition steps are relatively flat with little pucker. The main cau se of the difference in energies is because of steric interactions. The o ptimized structure of TS8 CB within the sum of their VDW radii (1.2 + 1.7 = 2.9) which are marked by dashed lines in Figure 1 6 TS9E CB also has two actions but f ive In addition, the distances of the interactions in TS9E CB are on average less than the distances in TS8 CB The other cyclobutene approaches to the active catalyst (TS14 CB and TS15 E CB ) share similar VDW steric interactions as TS8 CB and TS9E CB respectively but also contain the ones discussed previously The high % ee seen in the products is attributed to the approaches of cyclobutene to the active catalyst. Since there is only one favorable cyclob utene orientation only one enantiomer of each stereoisomer is formed The difference in free energy between TS8 CB and TS14 CB ( = 2.8 kcal/mol) gives a % ee of 98. This agrees with the experimentally observed % ee of 95. Other cyclobutene derivatives used in the experiment showed a low enantiomeric excess for the E stereoisomer product of cyclobutene. For these substrates, it is hypothesized that an approach analogous to TS14 CB or TS15E CB would not have a s high of an energy barrier The E active catalyst has its alkylidene substituent oriented toward the mesitylene cap, opening space below the Ru=C bond and allowing substituents on the cyclobutene substrates more space during cycloaddition. This would allow for the other enantiomer to be f ormed and explains the low % ee (< 85) observed in the experiment for E stereoisomer products This cyclobutene substrate, however, has only one favorable approach to the active catalyst

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60 which forms one enantiomer preferentially over the other and explain s the high enantiomeric excess of 95%. It should be noted that the large negative change in enthalpy during the coupling stage caused by a reduction of ring strain in the strained cyclo olefin would cause the reaction mixture to increase in temperature. This increase in temperature explains the overall better yields observed for cyclobutene derivatives and lower Z / E ratios. More energy provided to the system would allow energy barriers to be overcome easier, changing the calculated product ratios as the c atalytic cycle repeated and skew them closer to the experimental values

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61 CHAPTER V C ONCLUSION 5.1 Conclusion The initiation of 1cat has been shown to occur through the initial metathesis of a terminal olefin resulting in two active catalytic species that are poised to produce the Z and E products while formation of the Ru methylidene species ( 21 ) is energetically disfavored Therefore initiation and regeneration of the active catalytic species are the determining factors in the observed stereochemistry of the products. The turnover limiting step in the catalytic cycle for all of the AROCM reactions within this study are that o f cycloaddition to the active catalytic species. This step differentiates between the enantiomers of the stereoisomers. This differentiation occurs from the approach of the cyclo olefin substrate. For norbornene derivatives, there is only one favorable app roach which uses the exo face of the system and orients the bridging carbon away from the mesitylene cap, reducing steric interactions. Other approaches would yield enantiomers of the products but are energetically disfavored having stationary points on t he potential energy surface of 32 kcal/mol or greater This results in identical % ee s between both stereoisomers. As the catalytic cycle progresses for norbornene, the concentration of the Z active catalyst ( 7 ) would increase. This is caused by the two favorable path ways to regenerate 7 (releasing Z or E product), while there is only one to regenerate 4E This increases the probability of norbornene to couple to 7 and results in a Z / E ratio closer to the experimentally obtained results. For norbornene* favorable formation of 4E occurs

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62 while releasing either Z or E products*. This would increase the chances of norbornene* coupling to complex 4E and would increase the calculated Z / E product ratio closer to the experimental value. Cyclobutene derivatives, a less bulky substrate than norbornene, also ha ve only one energetically favorable approach Th is approach o rients the ether linked benzene groups away from the bulk of the catalyst and generates the main enantiomer product. A seco nd cyclobutene approach was located and would lead to the enantiomer of the products. Even though this approach is disfavored, the free energies are less than 30 kcal/mol, making them feasible. This second pathway, as well as the orientation of the alkylid ene ligand in the E active cataly s t, makes this second approach viable for other cyclobutene substrates This explains the lower % ee observed in the E CB products for other cyclobutene derivatives and terminal olefins tested 42 The orientation of the allyl group (R1) in the Z active catalyst forces the cyclobutene substituents to be in close proximity to R1 and increases steric effects of this second approach This is the reason that there is a large % ee (> 92 ) associated with the Z isomer of the cyclobutene products. The E active catalytic species has the alkylidene group oriented up toward the mesitylene cap, providing space for the ether linked groups on cyclobutene in this second approach This m akes the approach with the ether linked groups oriented under the bulk of the catalyst more favorable and allows for the enantiomer of the E product to be formed explaining the low % ee observed for this stereoisomer The increased yield seen for cyclob utene versus norbornene derivatives stems from the large amount of energy released from opening the strained cyclo olefin systems. Cyclobutene has greater ring strain then norbornene due to the 94 bond angles at the sp 2

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63 hybridized carbons, compared to 10 8 in norbornene. Norbornene forces its five membered ring to be in it s most favorable conformation, envelope, while the C C C bond angles of the six membered ring a re 108 and 102 respectively The increased ring strain of cyclobutene can be seen by the large enthalpy changes in the cyclobutene schemes in going from cycloaddition to a metallacyclobutane during the coupling phase This large negative enthalpy change release s heat, increasing the temperature of the solution, and provid es more energy for the system to overcome TS barriers. The increase in temperature from releasing ring strain in the cyclobutene system would also allow for more of the E products to be formed Energy barriers would be overcome easier with the additional heat allow ing for the formation of more E CB product, skewing the calculated Z / E ratio closer to the experimentally observed results. The origins of Z and enantioselectivity in the AROCM reactions of three cyclo olefin substrates with allyl acetate cat alyzed by a stereogenic at Ru complex have been elucidated. Hypotheses based on these mechanisms can be applied toward other AROCM systems and insights into the reaction mechanism should provide information to aid in the development of catalysts and metath esis systems. These advances should make targeted synthesis easier and reduce waste and by products.

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64 REFERENCES (1) Nobel Media AB. The Nobel Prize in Chemistry 1950. http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1950/ (accessed March 14, 2015). ( 2 ) Nobel Media AB. The Nobel Prize in Chemistry 1912. http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1912/ (accessed March 14, 2015). (3) Nobel Media AB. The Nobel Prize in Chemsitry 2005. http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2005/ (accessed March 15, 2015). (4) Chauvin, Y. Olefin Metathesis: The Early Days. http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2005/chauvin lecture.pdf (accessed March 11, 2015). (5) Philips Petro leum Co I. & E. C. Product Research and Development 1964, No. 3, 170. ( 6 ) Natta, G. Angew Chem ., Int. Ed. Engl 1964, No. 3, 723. (7) Fischer, E. O. Angew Chem 1964, No. 76, 645. ( 8 ) Hrisson, J. L.; Chauvin, Y. Makromolecular Chemistry 1971, 141, 161. (9) Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J Am Chem Soc 1978, 100 (11), 3611. ( 10 ) Howard, T. R.; Lee, J. B.; Grubbs, R. H. J. Am. Chem. Soc. 1980, 102, 6876. (11) Casey, C. P.; Burkhardt, T. J. J. Am. Chem. Soc. 1974, 96, 7809. ( 12 ) Schrock, R.; Rocklage, S.; Wengrovius, J.; Rupprecht, G.; Fellmann, J. J Mol Catal 1980, 8 (1 3), 73. (13) Wengrovius, J. H.; Schrock, R. R. J. Am. Chem. Soc. 1980, 102, 4515. ( 14 ) Murdzek, J. S.; Schrock, R. R. Organometallics 1987, 6, 1373. (15) Schaverien, C. J.; Dewan, J. C.; Schrock, R. R. J. Am. Chem Soc. 1986, 108, 2771. ( 16 ) Tebbe, F. N.; Parshall, G. W.; Ovenall, W. J. Am. Chem. Soc. 1979, 101, 5074. (17) Ott, K. C.; Lee, B. J.; Grubbs, R. H. J. Am. Chem. Soc. 1982, 104, 2942. ( 18 ) Straus, D. A.; Grubbs, R. H. Organometallics 1982, 1, 1658.

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65 (19) Novak, B. M.; Grubbs, R. H. Proc. ACS Div. Poly. Mat. Sci. Engr. 1987, 57, 651. ( 20 ) Novak, B. M.; Grubbs, R. H. J. Am.Chem. Soc. 1988, 110, 960. (21) Novak, B. M.; Grubbs, R. H. J. Am. Chem. Soc. 1988, 110, 7542. ( 22 ) Nguyen, S. T.; Johnson, L. K.; Gru bbs, R. H. J. Am. Chem. Soc 1992, 114, 3974. (23) Benson, S. W. Thermochemical Kinetics Methods for the Estimation of Thermochemical Data and Rate Parameters; John Wiley: New York, 1976. ( 24 ) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503. (25) This catalyst was initally not considered to be fesabl e to manufacture because one of the intermediate reactants was highly volatile A later advancment made by Grubbs et al. made it possible to manufacture. ( 26 ) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed Engl. 1995, 34, 2039. (27) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100. ( 28 ) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1, 953. (29 ) Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett 1999, 40, 2247. ( 30 ) Trnka, T. M.; Morgan, J. P.; Sanford, M. S.; Wihelm, T. E.; Scholl, M.; Choi, T. L.; Ding, S.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 2546. (31) Bielawski, C. W.; Grubbs, R. H. Angew. Chem., Int. Ed Engl. 2000, 39, 2903. ( 32 ) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, Jr., P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791. (33) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyd a, A. H. J. Am. Chem. Soc. 2000, 122, 8168. ( 34 ) Gessler, S.; Randl, S.; Blechert, S. Tetraheron Lett 2000, 41, 9973. (35) Dang, Y.; Wang, Z. X.; Wang, X. Organometallics 2012, 31, 7222. ( 36 ) Ibrahem, I.; Yu, M.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 3844. (37) (a) Endo, K.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133, 8525. (b) Keitz, B. K.;

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66 Endo, K.; Herbert, M. B.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133 9686. (c) Herbert, M. B.; Lan, Y.; Keitz, B.K.; Liu, P.; Endo, K.; Day, M. W.; Houk, K. N.; Grubbs, R. H. J. Am. Chem. Soc. 2012 134 7861. (d) Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M. B.; Grubbs, R. H. J. Am. Chem. Soc. 2012, 134 693. (e) Quigley, B. L.; Grubbs, R. H. Chem. Soc. 2013 5 501. (f) Rosebrugh, L. E.; Herbert, M. B.; Marx, V. M.; Keitz, B. K.; Grubbs, R. H. J. Am. Chem. Soc. 2013 135 1276. ( 38 ) Nelson, J. W.; Grundy, L. M.; Dang, Y.; Wang, Z. X.; Wang, X. Organometallics 2014, 33, 4290. (39) Dang, Y.; Wang, Z. X.; Wang, X. Organometallics 2012, 31, 8654. ( 40 ) Occhipinti, G.; Hansen, F. R.; Tornroos, K. W.; Jensen, V. R. J. Am. Chem. Soc. 2013, 135, 3331. (41) Liu, P.; Xu, X.; Dong, X.; Keitz, B. K.; Herbert, M. B.; Grubbs, R. H.; Houk, K. N. J. Am. Chem. Soc. 2012, 134 (3), 1464 1467. ( 42 ) Hartung, J.; Grubbs, R. H. J. Am. Chem. Soc. 2013, 135, 10183. (43) Cossy, J.; Arsenyadis, S.; Meyer, C. Metathesis in Natural Product Synthesis: Strategies, Substrates and Catalysts, 1st ed.; Wiley VCH: Weinheim, Germany, 2010. ( 44 ) Sutthasupa, S.; Shio tsuki, M.; Sanda, F. Polym. J. 2010, 42, 905. (45) Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864. ( 46 ) Leach, A. R. Molecular Modelling: Principles and Applications, 2nd ed.; Pearson Education Limited: Essex, 2001. (47) Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133. ( 48 ) Becke, A. D. Phys. Rev. A 1988, 38, 3098. (49) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. ( 50 ) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (51) (a) Zhao, Y.; Truhlar, D. G. Acc. Chem. Res. 2008, 41, 157. (b) Zhao, Y.; Truhlar, D. G. J. Chem. Theory Comput. 2009 5 324. (c) Kulkarni, A. D.; Truhlar, D. G. J. Chem. Theory Comput. 2011 7 2325. ( 52 ) They note that computational cost is difficult to directly compare and it has a lot of variables asso ciated with it..

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67 (53) Andrae, D.; Haeussermann, U.; Dolg, M.; Stoll, H.; Preuss, H. Theor Chim Acta 1990, 77, 123. ( 54 ) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J Phys Chem B 2009, 113, 6378. (55) Sliwa, P.; Handzlik, J. Chem. Phys. Lett. 2010, 493, 273. ( 56 ) Giri, R.; Lan, Y.; Liu, P.; Houk, K. N.; Yu, J. Q. J. Am. Chem. Soc. 2012, 134, 14118. (57) Herbert, M. B.; Lan, Y.; Keitz, B. K.; Liu, P.; Endo, K.; Day, M. W.; Houk, K. N.; Grubbs, R. H. J. Am. Chem. Soc. 2012, 134, 7861. ( 58 ) Lin M.; Kang, C. Y.; Guo, Y. A.; Yu, Z. X. J. Am. Chem. Soc. 2012, 134, 398. (59) Yeom, H. S.; Koo, J.; Park, H. S.; Wang, Y.; Liang, Y.; Yu, Z. X.; Shin, S. J. Am. Chem. Soc. 2012, 134, 208. ( 60 ) Frisch, M. J. In Gaussian09; revision D.01; Gaussian, Inc., Wallingford, CT 2009. ( 61 ) Plata, R. E.; Singleton, D. A. J. Am. Chem. Soc. 2015, ASAP.

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68 APPENDIX A FULL SCHEMES AND E XTRA FIGURES Scheme A 1. Initiation of C omplex 2 with R1 of the A llyl Acetate Oriented Towards Benzene Ring of the Hoveyda Ligand and Away from the M esitylene Cap Leading to the Ru methylidene C omplex 21 Scheme A 2. Initiation of C omplex 2 with R1 of the Allyl Acetate Oriented Towards Benzene Ring of the Hoveyda L igand and T owards the M esitylene C ap Leading to the Ru methylidene C omplex 21

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69 Scheme A3. Disassociative Cycloaddition TSs Leading from Complex 2 to Complex 7 or 4E W here the Nitrato Ligand is in a Monodentate Configuration Scheme A 4 High Energy Approaches of Norbornene for the Coupling to C omplex 7 or 4E via T wo E ndo Faces and One Exo Face of the N orbornene orbital.

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70 Scheme A 5 Possible P athways for the R elease of the Z product and Regeneration of C omplex 7 Scheme A 6 Possible Pathways for the R elease of the Z product and R egenerat ion of C omplex 4E

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71 Scheme A 7 Possible Pathways for the R elease of the E product and Regeneration of C omplex 7 Scheme A 8 Possible Pathways for the R elease of the E product and Regeneration of C omplex 4E

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72 Scheme A 9 High Energy Approaches of N orbornene* to C omplex 7 or 4E via Two Endo Faces and One Exo face (with Two Possible R5 O r ientations) of the N orbornene orbital.

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73 Figure A1. Structural analysis of high energy cycloaddition steps for the coupling of norbornene* to complex 7 and 4E with steric interactions marked by a dashed line all distances are given in , and hydrogens omitted fo r clarity except for those in question. VDW radii of H = 1.2 and C = 1.7 . Scheme A 10 Possible Pathways for the R elease of Z product and Regeneration of C omplex 4E from C omplex 13*

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74 Scheme A 11 High Energy R elease of Z product and R e generation of C omplex 7 from C omplex 12* where the R5 G roup is Oriented Toward the Bulk of the C atalyst. Scheme A 12 High Energy C ycloaddition Steps for the R elease of Z product and Regeneration of C omplex 4E from C omplex 12* where the R5 Group is O riented T oward the Bulk of the C atalyst.

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75 Scheme A 13 High Energy R elease of E product and R egeneration of C omplex 7 from C omplex 8E* where the R5 Group is Oriented Toward the B ulk of the C atalyst. Scheme A 14 High Energy R elease of E product and Regeneration of C omplex 4E from C omplex 8E* where the R5 G roup is Oriented T oward the B ulk of the C atalyst.

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76 Schem e A15 Release of Z CB product and Regeneration of C omplex 7 Scheme A16 Release of Z CB product and Regeneration of C omplex 4E

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77 Scheme A17 Release of E CB product and Regeneration of C omplex 7 Scheme A18 Release of E CB product and Regeneration of C omplex 4E

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78 APPENDIX B C ARTESIAN COORDINATES (), SCF ENERGIES AND FREE ENERGIES AT 298.15 K AND 1 ATM FOR THE OPTIMIZED STRUCTURES 3 B3LYP / SDD/6 31G(d) SCF energy in gas phase : 2149.8384452200 a.u. M06 / SDD/6 311++G(d,p) SCF energy in solution: 2148.9948746800 a.u Ru 0.019553 0.731307 0.211002 O 2.278201 2.401117 2.356563 O 1.224469 2.482643 1.096144 O 0.262594 2.740158 0.832352 N 1.221385 0.562042 2.467964 N 0.571560 1.752967 2.052761 C 0.141624 0.654856 1.644564 C 1.383984 1.7 12512 3.355897 C 2.265763 0.419926 2.165563 C 3.415993 0.220776 1.349670 C 4.432198 0.862086 0.937118 C 5.019853 1.516087 2.202917 C 3.879800 2.151835 3.024386 C 2.874346 1.050256 3.442241 C 3.178665 3.225064 2.161032 C 2.568324 2.565258 0.895310 C 1.535776 1.527638 1.379656 C 3.709391 1.922702 0.081310 C 1.921679 2.096757 1.711589 C 2.149553 3.237079 0.918389 C 3.470369 3.611625 0.649241 C 1.002170 4.050762 0.363836 C 0.998280 0.392277 0.937418 C 1.548564 0.143438 2.269175 C 1.454030 1.115274 2.905019 C 2.444549 4.756818 2.251589 C 0.009018 2.349377 3.284667 C 3.0 00238 3.509636 2.930425 C 2.215307 1.191871 2.981299 C 2.997154 1.367864 2.260015 C 4.559596 2.895476 1.154077 C 1.977877 1.345976 4.170894 C 4.504216 3.342352 2.711651 C 2.748135 0.952690 4 .255306 C 2.624916 0.306360 4.842525 C 4.299548 1.784554 1.963646 C 2.772428 0.154457 3.134065 C 5.977517 3.293551 0.818314 H 0.893439 2.041859 2.111613 H 1.194163 1.430206 0.649979 H 1.658800 1.406828 4.369375 H 2.163661 2.389472 2.978505 H 3.008962 0.715916 0.462224 H 3.913870 0.993007 1.954924 H 5.238002 0.398061 0.352229 H 5.553272 0.766677 2.805466 H 5.754478 2.284280 1.925290 H 4.291527 2.617108 3.929834 H 2.070943 1.475161 4.058275 H 3.391780 0.293801 4.051633 H 2.392354 3.726806 2.740596 H 3.907177 3.996987 1.874301 H 2.071262 3.331204 0.289260 H 3.3143 14 1.463851 0.830140 H 4.423117 2.698370 0.230527 H 3.650966 4.487020 0.028965 H 0.427059 4.539743 1.160528 H 0.295354 3.431805 0.199698 H 1.373555 4.836577 0.301061 H 0.960856 1.920052 2.37 4197 H 2.622591 4.716569 1.171363 H 2.932080 5.653407 2.649078 H 1.367001 4.841974 2.422458 H 0.017118 3.440157 3.213738 H 0.629149 2.079756 4.150015 H 2.773736 3.562067 4.003047 H 1.889385 2.326863 4.628164 H 4.878213 2.417707 3.160818 H 5.048701 4.183203 3.155888 H 4.726232 3.315178 1.639082 H 3.260252 1.737368 4.798600 H 3.043811 0.470378 5.832058 H 5.134033 1.222418 2.377567 H 2.100909 0.368685 3.973668 H 3.720815 0.197971 3.550384 H 2.324058 0.673302 2.572962 H 6.352244 2.720360 0.039647 H 6.656555 3.102553 1.656336 H 6.045905 4.355230 0.559109 C 1.731492 0.488999 1.423000 C 2.521605 0.382630 0.754043 H 1.560496 1.491791 1.055158 H 1.375399 0.265059 2.425016 H 2.977498 0.087122 0.184561 C 3.066934 1.637221 1.378167 H 2.482820 1.927028 2.257377 H 3.078213 2.461781 0.662932 N 0.940655 3.274208 0.121439 O 1.305435 4.436927 0.092138 O 4.427495 1.327371 1.760885 C 5.264644 2.295256 2.230672 O 6.399164 1.988227 2.509462 C 4.714003 3.700 313 2.385498 H 3.849085 3.718205 3.058082 H 4.383870 4.115438 1.426861

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79 H 5.504057 4.329234 2.796471 TS03 B3LYP / SDD/6 31G(d) SCF energy in gas phase : 2149.8333035200 a.u. M06 / SDD/6 311++G(d,p) SCF energy in solution: 2148.9962471300 a.u Ru 0.047008 0.789735 0.208993 O 2.277841 2.325939 2.253357 O 0.927030 2.782428 1.131598 O 0.067254 2.778997 0.795559 N 1.077260 0.828446 2.323065 N 0.775695 1.867778 1.783643 C 0.013527 0.759234 1.520516 C 1.197286 2.095319 3.046115 C 2.159664 0.145751 2.146940 C 3.252156 0.391374 1.188880 C 4.297874 0.710211 0.925957 C 4.960399 1.106106 2.260993 C 3.881423 1.628 751 3.232025 C 2.838424 0.514542 3.489179 C 3.201835 2.865632 2.606100 C 2.521108 2.471113 1.268550 C 1.458626 1.400750 1.587342 C 3.595320 1.934034 0.301262 C 2.163628 2.068166 1.474785 C 2.523451 3.096193 0.584323 C 3.882435 3.311812 0.328408 C 1.484806 3.972534 0.079237 C 0.643071 0.424597 1.134636 C 1.382858 0.134393 2.381025 C 1.307985 1.098916 3.054560 C 2.532937 4.668942 2.065449 C 0.219591 2.662906 2.902779 C 3.116817 3.409514 2.697152 C 2.223768 1.142392 2.937075 C 3.147561 1.307024 2.140869 C 4.881428 2.551683 0.942204 C 2.012287 1.340059 4.230668 C 4.570267 3.169527 2.286346 C 2.938138 0.894325 4.116238 C 2.826759 0.338927 4.759113 C 4.491331 1.565284 1.854825 C 2.779686 0.211949 3.116368 C 6.339477 2.768852 0.613809 H 0.830108 1.789399 2.401061 H 0.686437 1.490873 0.914999 H 1.487975 1.940625 4.088804 H 1.949863 2.741663 2.573279 H 2.792598 0.713525 0.249554 H 3.738440 1.271340 1.636245 H 5.060272 0.325973 0.234883 H 5.47 9737 0.240806 2.697904 H 5.719200 1.882263 2.092581 H 4.346565 1.904706 4.187730 H 2.078380 0.856386 4.204108 H 3.340416 0.358807 3.932791 H 2.455850 3.281883 3.296128 H 3.952939 3.649904 2. 434597 H 2.051976 3.359582 0.833490 H 3.140366 1.661681 0.657859 H 4.335652 2.719614 0.093723 H 4.165111 4.094939 0.371806 H 1.061103 4.700698 0.625747 H 0.646105 3.391843 0.476068 H 1.928975 4.540665 0.902197 H 0.685681 1.880551 2.635970 H 2.565743 4.598898 0.972474 H 3.108084 5.549254 2.371878 H 1.492052 4.808863 2.373169 H 0.236167 3.730273 2.667402 H 0.821647 2.503741 3.80706 6 H 3.038105 3.493813 3.788745 H 1.928757 2.302800 4.725846 H 4.958307 2.233910 2.699148 H 5.205698 3.989525 2.639817 H 4.648204 3.118563 1.194647 H 3.582269 1.653546 4.542856 H 3.386146 0. 511024 5.674868 H 5.254657 0.973747 2.355814 H 2.071042 0.555988 3.878543 H 3.671173 0.156054 3.632782 H 2.309686 0.638795 2.608497 H 6.670936 2.070847 0.165809 H 6.976666 2.604271 1.489543 H 6.521748 3.783557 0.245005 C 1.345075 0.231832 1.444611 C 2.081393 0.604475 0.529242 H 1.511715 1.301274 1.366083 H 1.248689 0.132218 2.464497 H 2.689117 0.089649 0.206511 C 2.770795 1.83447 7 1.069827 H 2.160052 2.339690 1.823425 H 2.997806 2.532980 0.260337 N 0.504326 3.467388 0.137535 O 0.632945 4.676982 0.058020 O 4.007088 1.373487 1.672771 C 4.931172 2.245946 2.157942 O 5.949557 1.803494 2.636049 C 4.626754 3.729659 2.068480 H 3.681266 3.979667 2.561825 H 4.542024 4.055791 1.025730 H 5.441634 4.272561 2.547953 4 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8422431100 a.u M06/SDD/6 311++G(d,p) SCF energy in solution: 2149.0115609200 a.u Ru 0.050722 0.761546 0.223535 O 2.093887 2.057332 2.236261 O 0.432443 3.316217 1.064404

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80 O 0.388955 2.619024 0.837823 N 1.045798 1.116925 2 .185678 N 0.791552 2.074079 1.480623 C 0.021714 0.946360 1.365789 C 1.164820 2.471363 2.727884 C 2.136493 0.143872 2.124517 C 3.200820 0.564617 1.076097 C 4.275245 0.531761 0.948464 C 4.956765 0.735425 2.316893 C 3.900391 1.152348 3.362033 C 2.835910 0.038999 3.491110 C 3.233302 2.466729 2.908448 C 2.540160 2.264624 1.534335 C 1.461254 1.181434 1.719147 C 3.597641 1.839908 0.494585 C 2.172591 2.247868 1.119128 C 2.509091 3.137062 0.082534 C 3.863841 3.318977 0.225592 C 1.462256 3.926497 0.669542 C 0.080165 0.363314 1.459025 C 0.954745 0.012120 2.614870 C 0.8142 34 1.161575 3.372306 C 2.449206 4.387104 1.998920 C 0.247666 3.015233 2.487976 C 3.008303 3.104903 2.607648 C 1.980529 0.919775 2.999463 C 3.177161 1.615054 1.884574 C 4.879177 2.667853 0.47 7428 C 1.632650 1.440880 4.465856 C 4.422431 2.796683 2.111339 C 2.801386 0.642098 4.097999 C 2.624771 0.534842 4.829008 C 4.512769 1.833978 1.540689 C 2.835604 0.703743 3.042244 C 6.330172 2.838904 0.095691 H 0.778070 1.486927 2.525886 H 0.124344 1.431347 1.272093 H 1.444381 2.461264 3.784802 H 1.924276 3.043421 2.176488 H 2.712602 0.740187 0.110322 H 3.665000 1.513319 1.384325 H 5.021553 0.220587 0.205582 H 5.458751 0.190506 2.632496 H 5.732323 1.509260 2.240924 H 4.382547 1.297050 4.337714 H 2.091187 0.303886 4.253565 H 3.316962 0.897597 3.810286 H 2.497530 2.80 0198 3.652328 H 3.989869 3.259966 2.829757 H 2.085079 3.210662 1.235909 H 3.128233 1.707134 0.487950 H 4.349206 2.633524 0.384308 H 4.127912 3.990656 1.039610 H 1.170386 4.826754 0.110708 H 0.551679 3.349502 0.846626 H 1.850635 4.261700 1.636322 H 0.061632 1.884545 3.084329 H 2.401526 4.302653 0.907246 H 3.090273 5.239072 2.250184 H 1.441414 4.586627 2.375766 H 0.257105 4.039131 2.105222 H 0.861181 2.985237 3.397607 H 3.003893 3.203280 3.700877 H 1.494306 2.362712 5.022777 H 4.789743 1.843694 2.502451 H 5.116044 3.585878 2.423795 H 4.433680 2.741713 1.017203 H 3.583667 1.331058 4.392031 H 3.272279 0.735024 5.678519 H 5.289378 1.333070 2.114518 H 2.256820 1.221904 3.816589 H 3.747317 0.323532 3.511962 H 2.237619 0.155940 2.720415 H 6.685332 1.974787 0.480269 H 6.970639 2.923153 0.980860 H 6.480924 3.731439 0.519986 C 1.434845 0.134077 1.474980 C 1.936064 0.832962 0.162380 H 2.036712 0.770172 1.591601 H 1.589724 0.804213 2.320941 H 2.56 1086 0.169676 0.426915 C 2.667427 2.142525 0.365445 H 2.154370 2.795081 1.076195 H 2.777405 2.665945 0.587505 N 0.045452 3.612676 0.060809 O 0.194086 4.762410 0.455504 O 3.973472 1.789428 0. 890172 C 4.923225 2.732789 1.133686 O 6.000344 2.374777 1.549733 C 4.569120 4.183309 0.865957 H 3.699668 4.500293 1.452135 H 4.321185 4.345316 0.189003 H 5.429326 4.797950 1.132224 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8390892000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2149.0082664200 a.u Ru 0.249744 0.523344 0.429901 O 0.530821 3.414553 0.241619 O 1.947126 0.993409 1.487491 O 0.684830 0.410024 2.561742 N 1.214337 1.196585 2.220581 N 0.776020 0.371435 2.602911 C 0.118351 0.675341 1.605519 C 1.190175 1.075288 3.679707 C 2.418652 1.503029 1.452251 C 3.491279 0.395658 1.621707 C 4.730850 0.720633 0.763459

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81 C 5.312281 2.086965 1.177191 C 4.241992 3.178487 0.973636 C 3.031196 2.863236 1.877620 C 3.804066 3.207479 0.507042 C 3.209376 1.827663 0.911496 C 1.978 663 1.597113 0.014791 C 4.309812 0.761174 0.716009 C 2.179796 0.077443 2.490873 C 2.615088 1.253840 2.659035 C 3.982639 1.525549 2.558895 C 1.650997 2.370752 2.985318 C 0.902031 1.204949 0.5 52110 C 0.625823 2.307354 1.509675 C 1.057980 2.309365 2.845646 C 1.528626 4.267794 2.218402 C 0.293064 0.797674 3.934644 C 1.528320 4.352024 0.696022 C 0.095913 3.447584 1.058639 C 3.112807 1.124955 2.351308 C 4.926003 0.518154 2.327343 C 0.820792 3.380490 3.705571 C 2.897029 4.029927 0.095890 C 0.325540 4.527528 1.916644 C 0.133587 4.494728 3.234441 C 4.470956 0.799901 2.249216 C 2.715072 2.586077 2.379834 C 6.391842 0.846496 2.168432 H 1.313614 2.486713 0.126296 H 1.035624 1.598389 0.447930 H 1.542098 1.988186 4.167868 H 1.825934 0.242418 4.009841 H 3.060639 0.5 66781 1.319215 H 3.777208 0.316765 2.680219 H 5.485097 0.063050 0.913798 H 5.635497 2.067674 2.228021 H 6.201249 2.313161 0.573493 H 4.651451 4.157402 1.255741 H 2.265889 3.646604 1.793939 H 3.355259 2.833377 2.928300 H 3.065164 4.004904 0.667291 H 4.667174 3.439295 1.146180 H 2.902542 1.863278 1.962380 H 3.951453 0.218746 1.035098 H 5.174344 1.016850 1.344272 H 4.320253 2.553485 2.671644 H 1.077255 2.151384 3.894285 H 0.925594 2.551919 2.187585 H 2.197175 3.303452 3.157389 H 1.588515 1.447321 3.233051 H 1.781383 3.253173 2.545680 H 2.271920 4.958480 2.631315 H 0.5 48168 4.531730 2.626323 H 0.464852 0.014779 4.678401 H 0.830702 1.698819 4.256919 H 1.219010 5.365983 0.409544 H 1.170471 3.338304 4.732700 H 2.865159 4.011354 0.996172 H 3.631188 4.780711 0 .411241 H 3.235138 3.045021 0.434244 H 0.873539 5.396469 1.573416 H 0.059228 5.341980 3.886989 H 5.190515 1.604396 2.111714 H 2.849651 2.998171 3.389406 H 3.347652 3.176232 1.708764 H 1.673865 2.748245 2.092496 H 6.639511 1.036569 1.115893 H 7.027084 0.021207 2.506759 H 6.665903 1.743109 2.734504 C 1.980579 0.134132 0.902496 C 1.523378 1.387847 0.735816 H 2.809464 0.276586 0.2067 22 H 2.334096 0.261007 1.924665 H 2.062184 1.853314 0.084726 C 1.665914 2.225710 1.988442 H 1.167120 1.760466 2.841350 H 1.232536 3.221341 1.823123 N 1.631667 0.482422 2.602060 O 2.162859 0.781362 3.658857 O 3.085928 2.375928 2.255484 C 3.544346 2.958140 3.395116 O 4.737390 3.084872 3.543646 C 2.524337 3.408712 4.425137 H 1.967889 2.555145 4.828841 H 1.790987 4.099380 3.994917 H 3.058177 3.903817 5.236658 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8337671600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2149.0049870400 a.u Ru 0.095383 0.591183 0.513766 O 1.793994 1.242754 2.700131 O 0.804630 3.861426 0.734627 O 0.722314 2.659221 0.324656 N 1.125517 1.841941 1.675819 N 0.726923 2.493173 0.702839 C 0.046712 1.395423 0.982782 C 1.250180 3.299494 1.706471 C 2.206817 0.9064 88 1.983669 C 3.308026 0.942450 0.890212 C 4.373711 0.132972 1.177896 C 5.006153 0.135563 2.558915 C 3.910255 0.095608 3.644645 C 2.859877 1.192966 3.355074 C 3.236575 1.292944 3.634599 C 2.598338 1.565775 2.246836 C 1.538058 0.477721 2.008613 C 3.698514 1.518312 1.167956 C 2.125668 2.535251 0.363950

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82 C 2.525552 2.916322 0.927627 C 3.898379 2.989977 1.208899 C 1.539920 3.279590 2.014498 C 0.211707 0.155731 1.454047 C 0.570035 0.788735 2.552370 C 0.339319 2.087257 3.033380 C 2.298000 3.546771 2.976969 C 0.154563 3.735960 1.271515 C 2.725792 2.130751 3.348411 C 1.583 447 0.022726 3.195355 C 3.087253 2.308932 1.378635 C 4.869289 2.722995 0.245458 C 1.059708 2.620918 4.100619 C 4.163567 1.833806 2.915904 C 2.302646 0.556796 4.270219 C 2.039134 1.851716 4.7 21217 C 4.438978 2.399877 1.049007 C 2.684116 1.962576 2.795140 C 6.341559 2.766150 0.578181 H 0.810345 0.501448 2.845128 H 0.255770 0.917423 1.610121 H 1.519981 3.661578 2.702566 H 2.021072 3.635914 0.999440 H 2.847505 0.776062 0.091457 H 3.773149 1.939419 0.869433 H 5.148620 0.087947 0.401199 H 5.510409 1.112686 2.564259 H 5.772956 0.620453 2.774026 H 4.357870 0.284804 4.629110 H 2.087332 1.203412 4.135763 H 3.345669 2.179951 3.358282 H 2.471015 1.348726 4.421169 H 3.981180 2.069108 3.859800 H 2.125610 2.550008 2.239801 H 3.261796 1.731766 0.185752 H 4.443590 2.3 01275 1.363015 H 4.208755 3.268602 2.214069 H 1.667887 4.328034 2.313397 H 0.506188 3.138844 1.696580 H 1.699017 2.670522 2.912249 H 0.408817 2.704846 2.553001 H 2.338651 3.686318 1.890468 H 2.968540 4.278019 3.441284 H 1.277715 3.747479 3.316525 H 0.145908 4.530585 0.519927 H 0.762518 4.077731 2.118031 H 2.625462 2.008969 4.434603 H 0.851984 3.631792 4.437938 H 4.442520 0.795977 3.116940 H 4.862243 2.486169 3.452464 H 4.280128 2.014873 1.842094 H 3.075372 0.021366 4.760892 H 2.609947 2.250057 5.555758 H 5.180061 2.206744 1.821481 H 2.096267 2.761135 3.264149 H 3.5 70665 1.801472 3.415113 H 2.075319 1.052830 2.837734 H 6.752479 1.751885 0.660150 H 6.913246 3.284235 0.200315 H 6.523381 3.275302 1.529843 C 1.626194 0.727924 1.039723 C 1.892741 0.793658 0 .527187 H 2.352183 0.001018 1.413781 H 1.795232 1.711615 1.469173 H 2.479299 0.061426 0.846226 C 2.521996 2.065753 1.053265 H 1.991126 2.944930 0.698925 H 2.531566 2.045128 2.151685 N 0.331967 3.785962 0.212201 O 1.110408 4.733391 0.165424 O 3.895213 2.071862 0.586778 C 4.618199 3.222621 0.492281 O 5.762550 3.149715 0.108938 C 3.942934 4.526600 0.871304 H 3.098771 4.745247 0.2077 85 H 3.552857 4.493274 1.895027 H 4.683605 5.322980 0.792780 TS4 B3LYP/SDD/6 31G(d) SCF energy in gas pha se: 2149.8127996500 a.u. M06/SDD/6 311++ G(d,p) SCF energy in solution: 2148.9837869800 a.u Ru 0.088291 0.644208 0.117647 O 2.427645 2.484828 1.336836 O 0.263009 4.029734 0.626872 O 0.263971 2.137905 1.643658 N 0.659018 0.597030 2.374694 N 0.916106 1.912076 1.601465 C 0.205771 0.764735 1.346613 C 0.73664 4 1.752779 3.269292 C 1.644460 0.485992 2.281178 C 2.910602 0.003272 1.530441 C 3.896031 1.163371 1.334289 C 4.306153 1.709079 2.717231 C 3.050249 2.194785 3.471287 C 2.074320 1.010404 3.668 147 C 2.368171 3.305847 2.647356 C 1.943532 2.758887 1.259789 C 0.935195 1.611988 1.481862 C 3.201912 2.268248 0.513115 C 2.167757 2.310915 1.014012 C 2.196144 3.365688 0.082774 C 3.427803 3.739181 0.471823 C 0.958638 4.141021 0.306240 C 0.141069 0.985109 1.764106 C 1.385974 0.702840 2.519459 C 1.463437 0.284812 3.517575 C 2.759415 4.749020 0.682242 C 0.563006 2.489882 2.917977

PAGE 90

83 C 3.449736 3.497202 1.213396 C 2.536395 1.508642 2.294711 C 3.371562 1.709954 1.452195 C 4.623681 3.118459 0.109379 C 2.619364 0.492227 4.261699 C 4.576383 3.024796 0.293453 C 3.701229 1.296 486 3.044658 C 3.740002 0.300675 4.020236 C 4.572967 2.116524 0.866775 C 3.412769 0.673429 2.556022 C 5.935801 3.507716 0.748863 H 0.124056 1.995277 2.117869 H 0.173811 1.915520 1.213495 H 0.783757 1.449979 4.318453 H 1.626138 2.359045 3.045574 H 2.621578 0.427932 0.560025 H 3.390444 0.811931 2.102332 H 4.785343 0.800973 0.800917 H 4.821474 0.928502 3.295888 H 5.014537 2.540007 2.599868 H 3.338998 2.582541 4.457249 H 1.188838 1.333167 4.232240 H 2.569056 0.220293 4.253878 H 1.489225 3.690748 3.182208 H 3.061003 4.150510 2.523853 H 1.461936 3.560020 0.697717 H 2.929568 1.889498 0.480524 H 3.894498 3.106103 0.353596 H 3.446554 4.544425 1.203902 H 1.035372 5.180714 0.037987 H 0.053007 3.709500 0.121600 H 0.835240 4.174531 1.394904 H 0.606848 0.920897 3.692470 H 2.327671 4.562422 0.307221 H 3.482484 5.566933 0.590817 H 1.958605 5.067471 1.356176 H 0.440463 3.574141 2.842578 H 1.359076 2.284115 3.645144 H 3.843101 3.713245 2.214248 H 2.64 3938 1.273291 5.014884 H 5.027920 2.094284 0.648576 H 5.362103 3.786730 0.234155 H 4.190112 2.849303 0.716262 H 4.585845 1.896412 2.872787 H 4.654419 0.149830 4.587782 H 5.495384 1.633101 1. 181349 H 3.615065 1.148995 3.525578 H 4.216358 0.047497 2.376325 H 2.478170 0.115715 2.649624 H 6.260135 2.750284 1.473964 H 6.733242 3.599153 0.002792 H 5.855718 4.461563 1.279915 C 1.119719 0.447499 2.018003 C 1.911561 0.971570 0.112226 H 1.998352 1.010828 1.725885 H 1.267780 0.325599 2.764244 H 2.635629 0.251446 0.271778 C 2.589662 2.209446 0.623874 H 2.381486 2.352101 1.69192 3 H 2.203294 3.091814 0.104851 N 0.228842 3.450539 1.614102 O 0.672918 4.042252 2.597663 O 4.005989 2.040338 0.405289 C 4.893094 3.044918 0.652257 O 6.062705 2.847658 0.421621 C 4.352238 4. 346907 1.209346 H 3.838921 4.188858 2.164482 H 3.625949 4.805873 0.529859 H 5.190865 5.027509 1.357732 5 B3LYP/SDD/6 3 1G(d) SCF energy in gas phase: 2149.8145267100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9846674600 a.u Ru 0.257990 0.596699 0.355628 O 2.842996 2.675194 1.071589 O 0.876346 4.032469 1.250747 O 0.056237 2.101279 1.942848 N 0.586505 0.408664 2.190426 N 0.725860 1.995686 1.427985 C 0.203498 0.755691 1.149741 C 0.825652 1.499068 3.136140 C 1.292377 0.877794 2.136063 C 2.681186 0.722126 1.466298 C 3.359912 2.098884 1.328617 C 3.539835 2.715387 2.730059 C 2.159910 2.872 852 3.401730 C 1.496750 1.483227 3.543675 C 1.275663 3.790322 2.532667 C 1.081792 3.168401 1.124525 C 0.368196 1.812165 1.301415 C 2.467185 3.010279 0.462232 C 1.918038 2.572946 0.860914 C 1.815693 3.630878 0.060454 C 2.991750 4.177089 0.592390 C 0.490837 4.237863 0.458378 C 0.710636 1.134146 1.907299 C 2.098796 0.685994 2.134199 C 2.407769 0.510327 2.810515 C 3.194568 5.001266 0.708352 C 0.308228 2.469328 2.767980 C 3.863068 3.630783 0.709714 C 3.178597 1.506164 1.698700 C 3.187707 2.140263 1.313715 C 4.256130 3.725854 0.214721 C 3.723072 0.898197 3.048686 C 4.471 905 3.273811 0.646503 C 4.500216 1.107466 1.936444 C 4.766889 0.086190 2.608964

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84 C 4.329265 2.716792 0.752696 C 3.364391 1.112661 2.413592 C 5.512466 4.305539 0.821302 H 0.529477 1.986062 1.905870 H 0.619753 2.053619 1.347390 H 0.770647 1.155533 4.172315 H 1.817781 1.944553 2.975017 H 2.569443 0.260827 0.477259 H 3.307851 0.045040 2.066211 H 4.339596 1.970215 0.849857 H 4.19266 2 2.079042 3.345242 H 4.030392 3.694763 2.651321 H 2.282997 3.309169 4.401868 H 0.526918 1.571336 4.051746 H 2.135428 0.833545 4.161503 H 0.299384 3.943142 3.012402 H 1.745104 4.780261 2.444 316 H 0.456772 3.835367 0.527849 H 2.367901 2.592285 0.546460 H 2.939042 3.995738 0.348544 H 2.909349 4.986010 1.316001 H 0.455996 5.296720 0.171186 H 0.350306 3.729676 0.014402 H 0.339978 4.200135 1.543609 H 1.602349 1.168687 3.113600 H 2.409428 5.052701 0.052938 H 3.935018 5.778578 0.490386 H 2.746313 5.212983 1.683754 H 0.015138 3.513372 2.722679 H 1.147637 2.401950 3.471303 H 4.636456 3.624026 1.487004 H 3.923840 1.832341 3.563604 H 4.904696 2.269282 0.643678 H 5.260397 3.987345 0.911357 H 3.700461 3.310791 1.424315 H 5.331043 1.714482 1.599728 H 5.800070 0.376 112 2.781165 H 5.304835 2.365352 1.082626 H 3.543147 1.608387 3.377724 H 4.231955 0.476636 2.211818 H 2.496688 0.460340 2.531989 H 6.006358 3.577324 1.477059 H 6.238338 4.584424 0.048502 H 5.295072 5.196505 1.418736 C 0.419975 0.621022 2.491413 C 2.080507 0.716100 0.282407 H 1.357344 1.158508 2.392868 H 0.391125 0.192150 3.206702 H 2.704829 0.020377 0.280182 C 2.918144 1.722237 1.021509 H 3.025111 1.412246 2.073410 H 2.453670 2.709897 1.003725 N 0.097002 3.410588 1.998364 O 0.631491 3.959031 2.825723 O 4.220239 1.724936 0.392540 C 5.110619 2.735848 0.590377 O 6.178333 2.678971 0.026295 C 4.706922 3.870178 1.512165 H 4.440105 3.499499 2.508242 H 3.834694 4.409789 1.127585 H 5.550879 4.555646 1.593808 TS05 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8247466300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9859538800 a.u Ru 0.323052 0.358666 0.471973 O 0.389897 3.476801 1.134865 O 1.598027 1.552520 0.368031 O 0.956080 0.745230 2.271884 N 1.339421 1.775526 1.836559 N 0.770539 1.449904 2.315503 C 0.184956 1.249134 1.347020 C 1.260517 2.161883 3.246706 C 2.598308 1.613814 1.103631 C 3.413795 0.413801 1.649087 C 4.707762 0.238225 0.825493 C 5.55 2981 1.524353 0.899801 C 4.735399 2.701572 0.331124 C 3.470891 2.889420 1.199921 C 4.343180 2.398926 1.133076 C 3.473815 1.112156 1.194680 C 2.193868 1.397896 0.369100 C 4.332700 0.048781 0.640861 C 2.192153 1.292727 2.215101 C 2.789526 0.144485 2.774799 C 4.177225 0.003300 2.689302 C 1.967499 0.896119 3.498957 C 1.369006 1.290754 0.235047 C 1.160470 2.583029 0.919284 C 1.48443 1 2.784573 2.270998 C 0.157457 4.076178 3.360056 C 0.253911 2.228547 3.459573 C 0.349426 4.454146 1.895706 C 0.666785 3.694714 0.185459 C 2.985583 2.322893 1.671494 C 4.986191 0.976369 2.091 599 C 1.332555 4.018780 2.894412 C 1.822164 4.472031 1.485932 C 0.518895 4.939454 0.811918 C 0.848088 5.097891 2.157135 C 4.371723 2.133266 1.605965 C 2.404621 3.642236 1.210227 C 6.478608 0.777382 1.968116 H 1.830580 2.373669 0.722812 H 1.367641 1.356578 0.844414 H 1.756100 3.118536 3.431356 H 1.733070 1.402331 3.885259 H 2.804549 0.494911 1.592887

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85 H 3.666469 0.585026 2.706022 H 5.280836 0.604961 1.233587 H 5.845330 1.734928 1.938874 H 6.481158 1.396610 0.326475 H 5.333849 3.621715 0.369769 H 2.888074 3.755359 0.857483 H 3.774050 3.087815 2.238980 H 3.794310 3.250262 1.559354 H 5.252742 2.270536 1.737291 H 3.204527 0.906097 2.237460 H 3.813104 1.004796 0.706640 H 5.246301 0.139137 1.245560 H 4.638984 0.889692 3.105095 H 1.621032 0.517117 4.470255 H 1.079433 1.195927 2.937695 H 2.563924 1.792464 3.692485 H 1.863300 1.950517 2.852318 H 0.585716 3.087904 3.560320 H 0.659703 4.805376 4.004966 H 0.905266 4.055490 3.621069 H 0.578157 1.78 8338 4.406795 H 0.630099 3.259580 3.414938 H 0.102927 5.441758 1.733655 H 1.587900 4.134511 3.943366 H 1.944525 4.668341 0.417710 H 2.356900 5.247835 2.046639 H 2.282776 3.502042 1.696052 H 0.138611 5.790630 0.260976 H 0.720074 6.070559 2.624398 H 4.985120 2.917241 1.166183 H 2.504314 4.402072 1.997420 H 2.941260 4.021064 0.334029 H 1.345271 3.569655 0.955252 H 6.729145 0.245638 1.040821 H 7.010575 1.734242 1.947796 H 6.874322 0.184475 2.799641 C 2.039302 0.193428 0.802236 C 0.825494 1.576282 1.337833 H 2.626908 0.441836 0.153915 H 2.387661 0.242271 1.829134 H 1.51 7776 2.293231 0.886338 C 0.810392 1.727368 2.833801 H 0.379186 0.856344 3.332587 H 0.179745 2.603256 3.060310 N 1.617789 1.659358 1.646323 O 2.225752 2.540001 2.226386 O 2.157691 1.974771 3. 299152 C 2.444210 2.121386 4.624467 O 3.587923 2.336098 4.946494 C 1.302562 1.996848 5.615555 H 0.855649 0.996783 5.581067 H 0.504384 2.717159 5.405128 H 1.699673 2.178304 6.614481 TS06 B3LYP/SDD /6 31G(d) SCF energy in gas pha se: 2149.8146075700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9831917600 a.u Ru 0.011296 0.633655 0.255276 O 2.060833 1.848901 2.145362 O 0.893722 3.457818 1.755927 O 0.616747 2.631888 0.366550 N 0.936617 1.422026 2.028387 N 0.811076 2.337296 1.064993 C 0.063259 1.186690 1.143747 C 1.054995 2.828113 2.415608 C 1.958316 0.388798 2.233776 C 3.145806 0.588664 1.25819 3 C 4.151338 0.568356 1.407757 C 4.676467 0.597723 2.857882 C 3.493650 0.800169 3.828472 C 2.503873 0.380431 3.678834 C 2.792027 2.135059 3.495494 C 2.253978 2.102367 2.041805 C 1.235267 0. 948758 1.945455 C 3.438332 1.893426 1.076235 C 2.174957 2.450059 0.618413 C 2.464544 3.102496 0.593423 C 3.803164 3.204637 0.998120 C 1.395274 3.731939 1.456357 C 0.224240 0.311186 1.791036 C 0.877710 0.147518 2.675510 C 0.804205 1.337718 3.419254 C 2.370768 4.209106 2.159024 C 0.321797 3.369074 2.007933 C 3.019832 2.870353 2.494668 C 2.025197 0.672222 2.854056 C 3.222919 1.995463 1.454900 C 4.852583 2.706059 0.226909 C 1.821444 1.735067 4.281041 C 4.337862 2.666520 1.745816 C 3.046729 0.273210 3.725925 C 2.945930 0.926334 4.430634 C 4.538728 2.119335 1.005390 C 2.972068 1.421389 2.833875 C 6.285281 2.788449 0.697680 H 0.499063 1.086653 2.754051 H 0.201299 1.376693 1.603027 H 1.256605 2.938599 3.484311 H 1.868286 3.316527 1.859959 H 2.767454 0.64 0873 0.228858 H 3.640051 1.549458 1.467762 H 4.989054 0.410237 0.715145 H 5.205013 0.338071 3.091365 H 5.402347 1.413062 2.977926 H 3.863659 0.821634 4.862071 H 1.670460 0.275540 4.386670 H 3.021492 1.322636 3.915473 H 1.967255 2.314359 4.199434

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86 H 3.502923 2.964310 3.620297 H 1.760091 3.049319 1.805568 H 3.077350 1.891164 0.041813 H 4.144785 2.730348 1.164650 H 4.024268 3.692650 1.945393 H 1.538137 4.819100 1.508511 H 0.392668 3.539548 1.072679 H 1.441584 3.354524 2.484594 H 0.069180 1.969768 3.314512 H 2.141478 4.267749 1.088902 H 3.050484 5.031347 2.408255 H 1.442301 4.343683 2.721589 H 0.275612 4.346285 1.518822 H 1.000650 3.448551 2.866660 H 3.190431 2.824957 3.577433 H 1.732296 2.669215 4.826278 H 4.758956 1.673719 1.926831 H 5.072856 3.414758 2.064395 H 4.182107 2.775478 0.667521 H 3.930423 0.884981 3.856558 H 3.752512 1.220022 5.096954 H 5.342634 1.743565 1.634856 H 2.959802 2.217165 3.591343 H 3.772077 0.728417 3.112289 H 2.022 071 0.886449 2.905758 H 6.667176 1.795498 0.966154 H 6.941728 3.184405 0.085970 H 6.381938 3.431577 1.577955 C 1.468817 0.329075 1.629036 C 1.801339 1.009770 0.594235 H 2.334331 0.289567 1.4 20071 H 1.663561 1.305608 2.056602 H 2.546896 0.241978 0.809645 C 2.382372 2.389296 0.711907 H 1.891883 3.085440 0.034759 H 2.241873 2.729746 1.751430 N 0.260703 3.512467 1.261679 O 1.075806 4.374779 1.573533 O 3.796541 2.290650 0.440295 C 4.532629 3.370442 0.045173 O 5.712428 3.210007 0.159257 C 3.823316 4.700497 0.112623 H 3.061304 4.654546 0.898734 H 3.319144 4.997599 0.814085 H 4.570798 5.450305 0.373268 6 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8165601600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9857809100 a.u Ru 0.126259 0.601022 0.059259 O 2.560709 2.350375 1.300929 O 1.153375 2.432597 2.758464 O 0.492486 2.247976 1.293252 N 0.671983 0.639187 2.396695 N 0.858151 2.011196 1.625293 C 0.193822 0.840049 1.377492 C 0.788467 1.789158 3.295785 C 1.541412 0.5465 44 2.366647 C 2.874218 0.234895 1.639997 C 3.728943 1.512566 1.532867 C 4.023813 2.047038 2.949532 C 2.694092 2.364398 3.664311 C 1.861940 1.065628 3.785183 C 1.922251 3.425925 2.849731 C 1.613515 2.881545 1.430807 C 0.730698 1.624972 1.592227 C 2.947180 2.564927 0.723114 C 2.103881 2.417127 1.032958 C 2.122696 3.491963 0.124741 C 3.345827 3.864272 0.447601 C 0.881857 4.283172 0.220440 C 0.129829 1.142827 1.852065 C 1.347811 0.777901 2.603061 C 1.327823 0.156995 3.652660 C 3.045271 4.567751 0.591770 C 0.482553 2.578111 2.940207 C 3.651508 3.283275 1.148358 C 2.578 203 1.426380 2.315097 C 3.307353 1.790475 1.430657 C 4.541430 3.218718 0.127775 C 2.468585 0.470197 4.382239 C 4.733203 2.710023 0.232075 C 3.727429 1.114013 3.053170 C 3.670235 0.168340 4.0 77091 C 4.500276 2.194841 0.825504 C 3.364083 0.746166 2.526247 C 5.843183 3.604379 0.790224 H 0.111247 1.897347 2.247350 H 0.236591 2.025246 1.234332 H 0.817413 1.481434 4.343991 H 1.701450 2.362080 3.079799 H 2.663372 0.167339 0.638916 H 3.421059 0.547296 2.187885 H 4.672508 1.273604 1.024069 H 4.598526 1.307589 3.526120 H 4.640980 2.953204 2.887006 H 2.899129 2.746949 4.672884 H 0.926631 1.256493 4.328680 H 2.432379 0.320910 4.361031 H 0.988794 3.692056 3.365248 H 2.522707 4.344505 2.784099 H 1.073652 3.639070 0.852793 H 2.754875 2.208417 0.293565 H 3.544494 3.4 82773 0.631518 H 3.358695 4.683930 1.163384 H 0.925349 5.282686 0.232714 H 0.027953 3.794899 0.132443 H 0.793577 4.427193 1.303003

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87 H 0.392576 0.645113 3.902960 H 2.589109 4.385326 0.387820 H 3.821225 5.331581 0.470853 H 2.276064 4.957287 1.265300 H 0.313942 3.655932 2.863446 H 1.287663 2.407017 3.666800 H 4.068273 3.491764 2.141483 H 2.417607 1.209914 5.174437 H 5.128067 1.763062 0.610929 H 5.566146 3.416637 0.140382 H 4.323636 2.529353 0.767659 H 4.672990 1.593209 2.831574 H 4.573756 0.065234 4.633787 H 5.424397 1.696587 1.111235 H 3.607962 1.214420 3.489943 H 4.146600 0.009310 2.319628 H 2.422104 0.207691 2.649961 H 6.119277 2.879164 1.566520 H 6.667104 3.631279 0.068320 H 5.775264 4.587643 1.266427 C 1.127657 0.629582 2.026668 C 1.872878 1.102351 0.138234 H 1.974006 1.137458 1.578462 H 1.349355 0.175053 2.717284 H 2.699797 0.384167 0.183773 C 2.338480 2.526335 0.235816 H 1.874377 3.128184 0.545291 H 2.033902 2.939797 1.209623 N 0.01 1234 2.733311 2.411540 O 0.735222 3.481845 3.062637 O 3.775386 2.563172 0.181320 C 4.479320 3.382435 0.656234 O 5.683004 3.282454 0.658585 C 3.717173 4.371365 1.514840 H 3.031707 3.868084 2. 205828 H 3.123368 5.057440 0.899355 H 4.449287 4.946544 2.082422 7 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 1647.0358422500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1646.4082059400 a.u Ru 0.373918 0.488084 0.345058 O 0.215851 0.401539 2.418488 O 0.494748 2.324819 1.697083 N 1.471520 1.856866 0.849454 N 0.652554 2.308894 0.502103 C 0.294297 1.345903 0.395104 C 1.413439 3.310430 1.024957 C 2.66696 8 1.040754 0.594053 C 3.196121 1.265967 0.848227 C 4.358463 0.298152 1.143768 C 5.493854 0.551794 0.130792 C 4.966463 0.322873 1.301115 C 3.811530 1.313098 1.589898 C 4.469478 1.134841 1.426 648 C 3.319282 1.390226 0.416867 C 2.173152 0.422219 0.767484 C 3.850004 1.152152 1.012277 C 2.048833 2.168264 0.196088 C 2.479704 2.360614 1.130674 C 3.843004 2.223618 1.409431 C 1.514076 2.704271 2.240429 C 0.108588 3.541520 1.111705 C 2.966627 1.891511 1.227115 C 4.776683 1.911723 0.416507 C 4.318982 1.762018 0.895528 C 2.538895 1.759536 2.671767 C 6.236676 1.721653 0.754880 H 1.934002 0.548177 1.828007 H 1.940429 3.631772 1.927323 H 1.854852 3.830861 0.162386 H 2.381004 1.109276 1.570902 H 3.527476 2.307531 0.968531 H 4.725370 0.473271 2.163448 H 5.874714 1.577 339 0.237018 H 6.335523 0.124210 0.331967 H 5.773443 0.499708 2.023933 H 3.443493 1.188102 2.616864 H 4.179452 2.345838 1.495061 H 4.120723 1.330614 2.449768 H 5.303470 1.824968 1.235372 H 2.969953 2.426103 0.512194 H 3.058620 1.347590 1.747401 H 4.664536 1.855789 1.231505 H 4.182393 2.364379 2.433400 H 0.784643 3.460353 1.928619 H 0.954176 1.821396 2.566606 H 2.053701 3.094138 3.109095 H 0.442715 4.423884 0.559135 H 0.447865 3.635472 2.151122 H 5.031044 1.531612 1.685225 H 2.538014 2.734831 3.178189 H 3.229377 1.112788 3.221772 H 1.533031 1.340893 2.770322 H 6.454157 0.667616 0.971600 H 6.884345 2.022322 0.075635 H 6.522792 2.302173 1.638334 N 0.043131 1.660798 2.691616 O 0.131348 2.121604 3.794012 C 0.714696 1.191045 0.933300 H 1.322710 0.586974 1.615942 C 0.957552 2.666659 1.092448 H 0.428673 3.018727 1.994683 H 0.590026 3.232390 0.233249 O 2.377033 2.864784 1.280253 C 2.940314 4.104360 1.253588 O 4.122617 4.206894 1.477281 C 2.04 6817 5.286688 0.926204

PAGE 95

88 H 1.185096 5.346365 1.599929 H 1.659674 5.213331 0.096747 H 2.642492 6.195268 1.017098 TS7 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8161023300 a.u. M06/SDD/6 311++G(d,p) SCF energy in sol ution: 2148.9816263500 a.u Ru 0.031613 0.753093 0.213118 O 2.321904 2.207623 2.145948 O 0.921862 3.275330 2.286568 O 0.226654 2.831250 0.451183 N 0.911371 0.882328 2.406482 N 0.749044 2.045130 1.5 70457 C 0.050859 0.870028 1.447140 C 1.031952 2.163085 3.106496 C 1.970097 0.129917 2.371858 C 3.196863 0.395930 1.578745 C 4.254855 0.715723 1.448898 C 4.707154 1.150060 2.857856 C 3.490062 1.672713 3.650206 C 2.440091 0.543894 3.785763 C 2.881303 2.876574 2.900352 C 2.414635 2.441023 1.487173 C 1.351500 1.341112 1.655846 C 3.632600 1.911445 0.701568 C 2.038518 2.398005 1.035974 C 2.123951 3.288528 0.048456 C 3.394392 3.661591 0.510273 C 0.901559 3.865231 0.725154 C 0.533075 0.370542 1.215741 C 1.329180 0.066430 2.410609 C 1.238167 1.139749 3.129512 C 2.735578 4.5 22565 1.851781 C 0.284526 2.847231 2.725673 C 3.268388 3.241893 2.484483 C 2.251207 1.053456 2.877065 C 3.209323 1.946166 1.689807 C 4.566917 3.191318 0.080172 C 2.006994 1.375062 4.264942 C 4.665068 2.878787 1.978321 C 3.031563 0.805336 4.012017 C 2.904558 0.401767 4.701444 C 4.449425 2.342877 1.188378 C 3.155371 1.049108 2.907356 C 5.926591 3.574485 0.453792 H 0.547232 1.746180 2.315814 H 0.437562 1.445669 1.070738 H 1.143560 2.024484 4.185398 H 1.904963 2.720863 2.741258 H 2.866975 0.730279 0.587888 H 3.630548 1.264319 2.096227 H 5.116211 0.329146 0.887381 H 5.1 71508 0.304120 3.385315 H 5.470062 1.936603 2.783619 H 3.808737 1.980865 4.654769 H 1.577961 0.889522 4.372242 H 2.882513 0.308461 4.322967 H 2.034072 3.287900 3.466148 H 3.629100 3.678349 2 .820721 H 1.975885 3.290870 0.960995 H 3.326203 1.610776 0.307875 H 4.378196 2.710524 0.587366 H 3.461409 4.343282 1.355826 H 1.078094 4.909450 1.005669 H 0.017738 3.824243 0.084942 H 0.652408 3.323319 1.645982 H 0.523417 1.885845 2.805442 H 2.676916 4.416923 0.762810 H 3.401329 5.361556 2.080739 H 1.737113 4.757323 2.232483 H 0.162474 3.895528 2.437972 H 1.022218 2.801818 3.535914 H 3.278499 3.368093 3.574560 H 1.900665 2.311906 4.803129 H 5.013415 1.930160 2.396579 H 5.383651 3.659117 2.253612 H 4.656138 2.787229 0.886499 H 3.742872 1.541007 4.366471 H 3.5164 42 0.573148 5.583248 H 5.350790 1.972552 1.671699 H 2.958415 1.623390 3.822653 H 4.112268 0.538089 3.047597 H 2.374454 0.286768 2.829433 H 6.424075 2.710832 0.912330 H 6.583264 3.936692 0.34 5972 H 5.853030 4.359136 1.213243 C 1.636023 0.174981 1.428349 C 2.170874 0.687580 0.216353 H 1.774215 0.878676 1.648454 H 1.526371 0.837991 2.280143 H 2.650261 0.029067 0.436928 C 2.838568 2.044482 0.156986 H 2.476408 2.687401 0.954422 H 2.679339 2.529589 0.814606 N 0.294740 3.692650 1.282990 O 0.139845 4.886745 1.040246 O 4.258111 1.794213 0.309086 C 5.120364 2.792299 0.649175 C 4.547068 4.170172 0.921430 H 3.865823 4.159124 1.779733 H 3.977054 4.547094 0.064920 H 5.377606 4.845427 1.128740 O 6.298685 2.532301 0.722893 TS3E B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8248439500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9915299200 a.u Ru 0.127725 0.806483 0.485449

PAGE 96

89 O 2.406121 3.136747 0.416473 O 0.617992 3.026956 1.008809 O 0.764250 1.941909 2.286509 N 0.749 180 0.473761 2.317517 N 1.096789 0.683772 2.094326 C 0.228810 0.152994 1.435816 C 0.696588 0.282375 3.570446 C 1.924706 1.227979 1.868522 C 3.097046 0.279830 1.510967 C 4.267028 1.097868 0.9 28920 C 4.753911 2.104661 1.990419 C 3.593638 3.047291 2.371221 C 2.424112 2.216566 2.951814 C 3.131315 3.808020 1.110870 C 2.628745 2.801045 0.043754 C 1.435529 2.035904 0.649622 C 3.782296 1.847928 0.328851 C 2.472408 0.950845 1.776492 C 2.854539 2.246142 1.380526 C 4.206010 2.489261 1.107932 C 1.854880 3.375322 1.277420 C 0.768945 0.981465 0.851197 C 1.721135 1.418987 1.896606 C 1.845066 0.780972 3.143565 C 2.382870 4.997295 1.044199 C 0.710859 0.885517 3.511161 C 3.183230 4.290727 0.045268 C 2.557913 2.543012 1.641167 C 3.440036 0.054138 1.989113 C 5.183034 1.5 00884 1.252032 C 2.743927 1.224318 4.110845 C 4.575222 3.871682 0.430080 C 3.469733 2.979760 2.609669 C 3.556108 2.323905 3.838931 C 4.779922 0.244820 1.720902 C 3.054427 1.438441 2.462453 C 6.621788 1.764515 0.877443 H 0.719695 2.777979 1.033423 H 0.622847 1.771920 0.115520 H 0.846059 0.365682 4.438538 H 1.476496 1.055266 3.583415 H 2.759086 0.472188 0.792094 H 3.429707 0.253922 2.413889 H 5.085613 0.415352 0.663622 H 5.119850 1.571154 2.879733 H 5.597146 2.689967 1.599465 H 3.932166 3.761196 3.133864 H 1.599724 2.874014 3.258180 H 2.768567 1.678317 3.847805 H 2.330486 4.515555 1.364223 H 3.966707 4.399846 0.710487 H 2.317336 3.356027 0.845744 H 3.450893 1.136296 1.093741 H 4.613612 2.422030 0.761641 H 4.500920 3.480476 0.771032 H 1.605834 3.774102 2.270506 H 0.915071 3.058693 0.817409 H 2.264578 4.202680 0.690144 H 1.224355 0.083071 3.348784 H 2.254964 4.340194 1.911711 H 2.904203 5.903110 1.371839 H 1.392504 5.280156 0.674169 H 0.73 6303 1.948080 3.768952 H 1.414439 0.361369 4.169570 H 3.262128 4.958303 0.913024 H 2.810948 0.710230 5.064872 H 5.115387 3.317442 0.342751 H 5.168407 4.753409 0.698072 H 4.492063 3.229493 1. 313897 H 4.116007 3.827941 2.419079 H 4.266875 2.679669 4.580125 H 5.529407 0.528909 1.875793 H 2.508933 1.414381 3.413048 H 3.945845 2.055089 2.611936 H 2.407290 1.949523 1.739806 H 6.804758 1.462453 0.162010 H 7.312615 1.199802 1.513155 H 6.870832 2.827376 0.961864 N 0.097382 3.029799 2.068240 O 0.160079 3.981181 2.827283 C 1.101827 0.876264 1.558433 C 1.574619 0.471365 1.76561 2 H 0.760838 1.395166 2.450205 H 1.660477 1.498199 0.867340 H 1.319981 0.895392 2.736946 C 2.917613 0.936436 1.280065 H 3.073059 0.705858 0.229572 H 2.997974 2.014444 1.435574 O 3.935463 0. 230116 2.044591 C 5.234273 0.616995 2.012870 O 6.079973 0.135275 2.444093 C 5.558690 1.996990 1.468692 H 5.245423 2.103699 0.424998 H 5.048854 2.777169 2.045233 H 6.636822 2.143524 1.540027 3E B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8321776800 a.u. M06/SDD/6 311++ G(d,p) SCF energy in solution: 2149.0052273200 a.u Ru 0.222060 0.790371 0.437894 O 2.173858 3.016533 0.367154 O 0.036105 3.273642 1.371193 O 1.088333 1.617474 2.252521 N 0.682793 0.478080 2.376919 N 1.197956 0.612721 2.127216 C 0.281930 0.169373 1.471441 C 0.575201 0.265785 3.634665 C 1.914446 1.136301 1.926650

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90 C 2.996305 0.091595 1.541974 C 4.240502 0.807894 0.982332 C 4.810792 1.749770 2.061362 C 3.740726 2.790428 2.453830 C 2.498940 2.064318 3.018472 C 3.343464 3.604490 1.206636 C 2.765338 2.660927 0.119214 C 1.50 9965 1.986948 0.702331 C 3.835595 1.618041 0.264800 C 2.551358 0.916375 1.748433 C 2.874304 2.194554 1.258764 C 4.207639 2.463965 0.919792 C 1.843256 3.287219 1.086816 C 0.292259 1.133642 1. 050178 C 1.304361 1.588011 2.044934 C 1.358876 1.108836 3.362852 C 2.239000 4.736908 1.257822 C 0.863690 0.783918 3.560012 C 2.995060 4.103953 0.093511 C 2.256882 2.572208 1.665350 C 3.566073 0.038852 1.988502 C 5.220755 1.517743 1.075115 C 2.297602 1.574477 4.282563 C 4.381228 3.603347 0.504651 C 3.199567 3.042116 2.586114 C 3.216300 2.544243 3.891343 C 4.879830 0.281506 1.639530 C 3.265176 1.389570 2.602162 C 6.632109 1.794913 0.617418 H 0.800829 2.758879 1.036694 H 0.181236 1.867259 0.257717 H 0.751666 0.377379 4.500751 H 1.306584 1.085176 3.660939 H 2.5903 88 0.609570 0.804105 H 3.271773 0.496872 2.430056 H 4.994504 0.057218 0.710917 H 5.122939 1.173340 2.944328 H 5.705801 2.260231 1.681336 H 4.140865 3.460819 3.225804 H 1.736448 2.790298 3.33 0505 H 2.785294 1.481563 3.906460 H 2.602842 4.371346 1.470206 H 4.222319 4.131695 0.810245 H 2.507181 3.262551 0.754046 H 3.448644 0.955334 1.047314 H 4.715511 2.127461 0.680837 H 4.454391 3.443879 0.516295 H 2.221757 4.234279 1.487968 H 0.902222 3.050692 1.587405 H 1.614346 3.456632 0.027513 H 0.662677 0.336665 3.667945 H 2.097750 4.006677 2.062950 H 2.799989 5.587598 1.659740 H 1.255249 5.090287 0.933686 H 0.963653 1.833308 3.852104 H 1.546888 0.192432 4.181233 H 3.084094 4.843703 0.712721 H 2.310169 1.175285 5.292252 H 4.886344 3.093287 0.320358 H 5.009909 4.44 1474 0.826842 H 4.294417 2.897360 1.337998 H 3.927418 3.791846 2.300182 H 3.956238 2.919210 4.593426 H 5.660742 0.458129 1.805269 H 3.119436 1.317846 3.688007 H 4.098618 2.080063 2.440043 H 2.362348 1.844533 2.183066 H 6.796421 1.361195 0.377556 H 7.369957 1.353207 1.296576 H 6.829298 2.869578 0.549841 N 0.705430 2.864854 2.307269 O 1.076782 3.571359 3.234518 C 1.158959 0.709880 1.600027 C 1.449609 0.813477 1.586422 H 1.188069 1.033632 2.644101 H 1.916234 1.237751 1.022733 H 1.217946 1.265120 2.552493 C 2.787578 1.298432 1.102044 H 2.970568 1.027320 0.065204 H 2.821766 2.386239 1.212274 O 3.812435 0.665747 1.916899 C 5.107176 1.065634 1.864345 O 5.960430 0.352779 2.343658 C 5.412808 2.414659 1.238914 H 5.100339 2.453957 0.190214 H 4.889228 3.219328 1.767500 H 6.488360 2.581998 1.302501 B3LYP/SDD/6 3 1G(d) SCF energy in gas phase: 2149.8264585900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9982799700 a.u Ru 0.389540 0.289574 0.808908 O 1.394109 3.060482 1.409006 O 2.662215 0.761947 0.749669 O 1.485523 0.402637 2.544609 N 0.629578 1.905339 1.562092 N 1.140818 0.688094 2.002765 C 0.222367 0.998942 1.019476 C 0.312154 2.303071 2.936455 C 1.7721 17 2.429237 0.811551 C 3.108492 1.879549 1.375764 C 4.296047 2.413016 0.546946 C 4.304157 3.953678 0.569576 C 2.981703 4.477383 0.025997 C 1.811513 3.979807 0.850446 C 2.821995 3.959174 1.473022 C 2.803224 2.402516 1.482208 C 1.581844 1.980397 0.644299

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91 C 4.151374 1.916327 0.903105 C 2.496872 0.246708 1.818711 C 2.874579 1.079599 2.086253 C 4.205172 1.456694 1.843745 C 1.9213 30 2.101756 2.660167 C 0.146895 1.682724 0.391883 C 0.626839 2.871320 0.822744 C 0.619039 3.368150 2.136255 C 1.833396 3.012025 3.732772 C 0.788719 1.300411 3.305256 C 2.352751 3.505248 2.38 6465 C 1.405068 3.572618 0.138484 C 3.473508 1.209839 1.465924 C 5.166111 0.553282 1.392720 C 1.325326 4.512332 2.501143 C 3.748228 2.968195 2.066922 C 2.108057 4.726389 0.223707 C 2.065559 5.193760 1.538394 C 4.785390 0.788628 1.249800 C 3.129534 2.680096 1.352777 C 6.568177 0.992896 1.046598 H 0.697538 2.514070 1.063392 H 0.359275 1.730647 0.668329 H 0.034523 3.344169 2.970357 H 1.188512 2.217521 3.585759 H 3.086857 0.784861 1.343893 H 3.216437 2.185483 2.426473 H 5.230853 2.031386 0.977715 H 4.428759 4.325225 1.596980 H 5.155556 4.331857 0.011852 H 2.983012 5.575440 0.026732 H 0.854709 4.377836 0.485505 H 1.945100 4.340685 1.880791 H 1.898594 4.356232 1.917288 H 3.654669 4.322079 2.091027 H 2.685419 2.047447 2.511681 H 4.225066 0.829014 0.933408 H 4.968744 2.317279 1.518311 H 4.489703 2.493240 2.013300 H 2.280033 2.436395 3.642257 H 0.913156 1.704342 2.782990 H 1.852424 2.990983 2.023952 H 0.059971 2.836152 2.898225 H 1.784574 1.91 7113 3.744610 H 2.502531 3.335199 4.537529 H 0.832940 3.408272 3.932688 H 0.430169 0.525429 3.994457 H 1.662634 1.775319 3.758482 H 2.363525 4.603418 2.402678 H 1.299795 4.861142 3.529035 H 4.080874 3.275330 1.072100 H 4.472486 3.334362 2.804089 H 3.743842 1.873409 2.092457 H 2.698757 5.265298 0.507303 H 2.621872 6.089107 1.802681 H 5.533172 1.523130 0.957056 H 2.931101 3.120592 2.338903 H 3.963280 3.239679 0.917330 H 2.241656 2.859572 0.738244 H 6.704235 1.003078 0.042614 H 7.318426 0.310303 1.462723 H 6.778405 1.999651 1.420652 N 2.592032 0.830731 2.015439 O 3.49 7488 1.254729 2.714538 C 1.380404 1.235728 1.231117 C 1.266943 0.200350 1.918535 H 1.543499 1.950680 2.038925 H 2.255432 1.218292 0.581143 H 0.938538 0.098422 2.960812 C 2.527993 1.017421 1. 855390 H 2.798600 1.257837 0.829215 H 2.395173 1.944260 2.426466 O 3.609214 0.230629 2.431195 C 4.861032 0.732502 2.564633 O 5.781837 0.025022 2.772089 C 5.032844 2.239995 2.492487 H 4.713081 2.638439 1.524001 H 4.435120 2.737376 3.265016 H 6.087006 2.471089 2.648333 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8229230000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9992215400 a.u Ru 0.299377 0.378688 0.783407 O 1.883125 2.536047 1.645336 O 0.291632 1.015055 4.110732 O 1.522169 0.092126 2.520858 N 0.618490 1.933478 1.608350 N 1.228202 0.831790 2.037550 C 0.292125 1.083176 1.06237 2 C 0.455601 2.138460 3.049950 C 1.859902 2.237290 0.888185 C 3.002487 1.282732 1.330106 C 4.270224 1.552092 0.496256 C 4.711266 3.015707 0.702556 C 3.578551 3.963305 0.255379 C 2.319828 3. 697224 1.112585 C 3.262420 3.712247 1.234017 C 2.817706 2.240751 1.442839 C 1.549207 2.015415 0.603368 C 3.953840 1.302397 0.990437 C 2.571446 0.338592 1.879856 C 2.883469 0.995762 2.195582 C 4.203824 1.435055 2.019742 C 1.867143 1.968298 2.748964 C 0.122671 1.560430 0.213431 C 1.114184 2.601346 0.598480 C 1.215625 3.141137 1.889979

PAGE 99

92 C 1.911407 2.654576 4.014613 C 0.947894 1.571560 3.289681 C 2.669675 3.030050 2.745392 C 1.994285 3.104626 0.397725 C 3.597253 1.245210 1.518943 C 5.219349 0.586911 1.580223 C 2.125022 4.151022 2.196535 C 4.080460 2.437671 2.719091 C 2.906333 4.121170 0.091185 C 2.966257 4.643799 1.201938 C 4.897552 0.760389 1.369733 C 3.331109 2.720627 1.302997 C 6.612236 1.098132 1.305442 H 0.771386 2.743846 0.916461 H 0.097230 1.62 5512 0.846339 H 0.538628 3.195655 3.317389 H 1.223426 1.585021 3.606355 H 2.674676 0.242459 1.205726 H 3.217017 1.432647 2.398578 H 5.068170 0.875303 0.829773 H 4.961196 3.194748 1.758392 H 5.619660 3.219324 0.120330 H 3.889980 5.006163 0.399982 H 1.509874 4.384722 0.833923 H 2.552493 3.874874 2.173055 H 2.475227 4.399304 1.575254 H 4.152375 3.920943 1.843624 H 2.600176 2.059098 2.497224 H 3.657160 0.261841 1.157946 H 4.848817 1.483894 1.600802 H 4.437376 2.476075 2.233538 H 2.229444 2.393141 3.693205 H 0.900821 1.496664 2.933714 H 1.701219 2.808316 2.064428 H 0.590293 2.741505 2.680808 H 1.807781 1.566125 4.091969 H 2.452113 3.010529 4.898299 H 0.912314 3.100571 4.016296 H 0.999978 0.895259 4.148238 H 1.691199 2.362914 3.437605 H 2.718051 4.124469 2.678730 H 2.176825 4.541136 3.208517 H 4.593021 2.654135 1.777741 H 4.680978 2.848587 3.538905 H 4.034301 1.349625 2.838390 H 3.578954 4.509216 0.846011 H 3.681689 5.431333 1.423519 H 5.683 393 1.451234 1.070207 H 3.358452 3.274090 2.251266 H 4.100220 3.162057 0.661209 H 2.356740 2.909440 0.843100 H 6.757729 1.223343 0.224831 H 7.376232 0.397934 1.662323 H 6.786829 2.067532 1.7 82797 N 1.301201 0.355025 3.784286 O 2.129043 0.054745 4.597016 C 1.204739 1.376072 1.059919 C 1.358617 0.003709 1.834354 H 1.211485 2.145092 1.832927 H 2.056858 1.492138 0.390580 H 1.086600 0.141598 2.881229 C 2.675014 0.718090 1.703619 H 2.854153 1.070973 0.690852 H 2.678116 1.569718 2.392852 O 3.733986 0.213731 2.046511 C 5.010183 0.196755 2.250499 O 5.895484 0.628270 2.270413 C 5.255752 1.676017 2.488923 H 4.925432 2.284097 1.640298 H 4.712395 2.023936 3.374951 H 6.325168 1.821287 2.643939 TS4E B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8147486600 a.u. M06/SDD/6 311++G(d,p) SCF e nergy in solution: 2148.9945698500 a.u Ru 0.261438 0.410855 0.760134 O 1.806543 2.678503 1.377361 O 2.079462 1.073468 4.182377 O 1.076252 0.176793 2.696436 N 0.537369 1.767732 1.759350 N 1.309468 0.6 22163 2.052718 C 0.351848 0.962135 1.122847 C 0.334178 1.863080 3.207246 C 1.793225 2.136031 1.100959 C 2.938210 1.177843 1.527375 C 4.233280 1.530971 0.770936 C 4.630417 2.986284 1.089136 C 3.495280 3.936223 0.654348 C 2.210067 3.587832 1.436987 C 3.243390 3.772617 0.857794 C 2.839685 2.307468 1.177548 C 1.540441 2.003712 0.414524 C 3.981073 1.365835 0.738200 C 2.650561 0.153539 1.821144 C 2.978437 1.198700 2.026156 C 4.293560 1.615083 1.772075 C 1.984529 2.216081 2.538649 C 0.015667 1.565187 0.358610 C 0.952937 2.618541 0.832842 C 0.985168 3.107505 2.147669 C 1.9 27614 2.885953 3.735581 C 1.061179 1.250588 3.370526 C 2.618531 3.243353 2.423271 C 1.848478 3.198468 0.104898 C 3.661345 1.092319 1.502893 C 5.290133 0.729427 1.363796 C 1.836431 4.139309 2 .532353 C 4.049682 2.705862 2.356916

PAGE 100

93 C 2.704333 4.237536 0.278274 C 2.693535 4.706269 1.592603 C 4.957417 0.628520 1.272015 C 3.385285 2.579858 1.424212 C 6.674439 1.208901 1.001654 H 0.768057 2.745023 0.714041 H 0.201028 1.702967 0.694841 H 0.386889 2.899739 3.551877 H 1.100841 1.287713 3.741778 H 2.640851 0.143075 1.313854 H 3.102906 1.257847 2.611975 H 5.032900 0.850703 1.0931 51 H 4.832018 3.102802 2.164023 H 5.557329 3.245742 0.560815 H 3.775207 4.974458 0.876385 H 1.395421 4.274573 1.170143 H 2.393249 3.698032 2.516041 H 2.454981 4.462763 1.189045 H 4.150894 4 .033740 1.418881 H 2.672115 2.223278 2.252798 H 3.725516 0.328647 0.976162 H 4.891338 1.601905 1.304449 H 4.538289 2.667936 1.897079 H 2.373160 2.695839 3.445408 H 1.018485 1.767269 2.775412 H 1.810817 3.012907 1.806038 H 0.343483 2.653969 2.893015 H 1.867553 1.797754 3.852205 H 2.490199 3.291231 4.583644 H 0.913359 3.295821 3.764329 H 1.111590 0.498381 4.163857 H 1.822365 2.0106 03 3.578646 H 2.619727 4.335692 2.315452 H 1.836679 4.486549 3.560993 H 4.509039 2.897700 1.383420 H 4.669088 3.177778 3.128460 H 4.054458 1.623612 2.526385 H 3.388815 4.684276 0.432208 H 3.368068 5.510008 1.875286 H 5.730900 1.345434 1.003184 H 3.444820 3.048193 2.415804 H 4.131520 3.079497 0.798256 H 2.395595 2.805088 1.016339 H 6.790992 1.227954 0.089544 H 7.448609 0.545064 1.403394 H 6.861640 2.219431 1.378127 N 2.160815 0.146097 3.366638 O 3.184805 0.517214 3.180947 C 1.308377 1.259664 1.177676 C 1.392216 0.161981 1.862779 H 1.360557 1.984092 1.991428 H 2.16 2337 1.374857 0.511661 H 1.074804 0.108744 2.905092 C 2.692098 0.912070 1.737404 H 2.916038 1.182908 0.708849 H 2.638219 1.817446 2.352030 O 3.751524 0.039950 2.212754 C 5.015965 0.492552 2. 405393 O 5.911759 0.310240 2.537156 C 5.230939 1.993069 2.490491 H 4.917555 2.500554 1.572156 H 4.653627 2.423543 3.316787 H 6.292343 2.175247 2.660692 TS5E B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8182892600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9860891100 a.u Ru 0.585108 0.180662 0.654621 O 3.308922 1.954596 0.306225 O 0.047772 2.312088 0.095561 O 0.357450 1.771507 2.156721 N 2.267 606 0.652752 1.549719 N 0.461797 1.891492 1.755320 C 1.047736 0.894389 1.000180 C 2.516243 1.359590 2.807291 C 3.018303 0.542998 1.143413 C 2.658778 1.741150 2.061382 C 3.399924 3.009071 1.5 90747 C 4.920888 2.762657 1.617386 C 5.261809 1.584668 0.682125 C 4.547082 0.314330 1.198908 C 4.795288 1.920138 0.752660 C 3.257577 2.146021 0.772985 C 2.603575 0.821645 0.311822 C 2.949072 3.341886 0.155899 C 0.940977 2.175693 1.890879 C 1.765053 1.232823 2.543752 C 3.115105 1.540958 2.734028 C 1.214339 0.078528 3.055487 C 1.748225 0.042022 0.823486 C 2.470950 0.933359 1.662191 C 2.434615 0.883366 3.066883 C 4.157728 2.601857 2.423378 C 1.338098 2.342699 2.862889 C 3.867206 3.085083 1.007316 C 3.259093 1.949789 1.059712 C 1.453062 3.431757 1.511165 C 3.662849 2.7 60326 2.322894 C 3.137288 1.780467 3.861913 C 2.903677 4.271038 0.973566 C 3.964287 2.858417 1.862134 C 3.903506 2.772917 3.251284 C 2.810260 3.695411 1.732120 C 0.602734 4.496279 0.853475 C 5.132556 3.055102 2.510380 H 3.082617 0.036397 0.913956 H 2.004250 0.022624 0.228135 H 3.484640 1.868453 2.789075

PAGE 101

94 H 2.518536 0.662073 3.655314 H 1.576155 1.906247 2.027544 H 2.932226 1.514893 3.102470 H 3.148478 3.841095 2.261966 H 5.257894 2.543384 2.641092 H 5.452638 3.667079 1.292370 H 6.345993 1.409475 0.687119 H 4.809169 0.555823 0.581274 H 4.881777 0.100651 2.225503 H 5.068012 1.106651 1.439311 H 5.315498 2.822237 1.105082 H 2.940435 2.378648 1.795636 H 1.885522 3.586153 0.152757 H 3.486018 4.230039 0.205753 H 3.752168 0.811949 3.229816 H 0.272822 0.057542 3.599504 H 1.015657 0.783978 2.240716 H 1.927305 0.547885 3.738924 H 1.822649 0.129178 3.551210 H 3.229008 2.329535 2.934200 H 4.646282 3.396285 2.998014 H 4.817712 1.728379 2.405897 H 0.796 495 2.305947 3.812953 H 1.657295 3.379420 2.700128 H 4.822272 3.354748 0.538429 H 3.076921 1.713434 4.943900 H 2.644123 4.552306 0.050550 H 3.354134 5.138259 1.470779 H 1.972277 4.012535 1.4 86731 H 4.558424 3.643881 1.412357 H 4.454346 3.491249 3.852461 H 3.208056 4.663246 1.433582 H 1.002082 5.492111 1.070092 H 0.596891 4.385703 0.238486 H 0.436734 4.469462 1.191526 H 5.718319 2.690595 1.656228 H 5.318553 4.130687 2.597499 H 5.528856 2.566832 3.407206 N 0.018140 2.692596 1.324110 O 0.203903 3.839819 1.667067 C 1.228154 1.260636 1.326558 C 0.817201 1.249124 1.863565 H 1.421154 1.521935 2.362994 H 1.198049 2.105501 0.653487 H 0.735420 0.968577 2.925270 C 1.325676 2.647278 1.718946 H 1.212555 3.025941 0.701139 H 2.399905 2.601136 1.955662 O 0.645538 3.5 25729 2.644069 C 1.143141 4.749570 2.985355 O 0.494799 5.452272 3.721191 C 2.496631 5.149897 2.426143 H 2.527632 5.072842 1.334045 H 3.291377 4.508765 2.825172 H 2.692069 6.180078 2.724597 TS6 E B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.7997823000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9727685200 a.u Ru 0.204553 0.643720 0.507734 O 2.196678 2.971688 0.126229 O 0.786176 3.098042 2.702027 O 1.323456 0.984718 2.307381 N 0.362934 0.643359 2.349489 N 1.395321 0.624735 2.020212 C 0.477359 0.185410 1.386434 C 0.193268 0.002402 3.652853 C 1.544107 1.427431 1.960996 C 2.765416 0.502255 1.719612 C 3.967856 1.331078 1.226455 C 4.324302 2.388114 2.291928 C 3.111312 3.312248 2.524670 C 1.921635 2.469173 3.038342 C 2.734178 4.003928 1.197764 C 2.365945 2.941399 0.129977 C 1.1 48108 2.147035 0.645648 C 3.587786 2.025191 0.096041 C 2.697171 1.001920 1.538223 C 2.912382 2.276111 0.982898 C 4.183937 2.582698 0.476735 C 1.847431 3.348415 0.958603 C 0.243540 1.651037 1 .279977 C 1.526384 1.989922 1.926936 C 1.803199 1.700775 3.273067 C 2.004413 4.558708 1.881808 C 1.161536 0.704378 3.480267 C 2.966455 3.932421 0.876738 C 2.503946 2.703978 1.185120 C 3.785094 0.113922 1.719447 C 5.248299 1.684752 0.544439 C 2.990178 2.096283 3.878835 C 4.159940 3.261111 1.557693 C 3.700225 3.102654 1.794296 C 3.937939 2.798091 3.134773 C 5.034057 0.470128 1.208345 C 3.651838 1.186076 2.487038 C 6.581694 1.988752 0.093149 H 0.356407 2.865249 0.900014 H 0.108149 2.114421 0.311224 H 0.192397 0.729093 4.465869 H 1.006894 0.716192 3.840379 H 2.5083 03 0.269991 0.979582 H 3.024586 0.026060 2.649687 H 4.824603 0.662522 1.067651 H 4.616348 1.899459 3.233184 H 5.187175 2.979723 1.958326 H 3.362481 4.066819 3.281969 H 1.055377 3.111878 3.24 5940

PAGE 102

95 H 2.202695 1.978445 3.982787 H 1.888910 4.688216 1.355048 H 3.578092 4.615265 0.847968 H 2.097175 3.443222 0.802371 H 3.362805 1.281477 0.868174 H 4.437215 2.618641 0.461539 H 4.339390 3.556375 0.016220 H 2.196218 4.233197 1.505734 H 0.915819 3.012240 1.416909 H 1.624038 3.672769 0.063747 H 1.077372 1.142496 3.850692 H 1.609703 3.795551 2.562339 H 2.520830 5.316933 2.480581 H 1.163283 5.034427 1.368392 H 1.149083 1.749330 3.805943 H 1.960916 0.192092 4.027324 H 3.313119 4.712317 0.187108 H 3.177310 1.845989 4.918123 H 4.814342 2.766556 0.834440 H 4.752222 4.00 3791 2.104590 H 3.812031 2.505455 2.270538 H 4.454745 3.640536 1.233768 H 4.873621 3.109843 3.591163 H 5.865541 0.222614 1.325279 H 3.832996 1.028132 3.558907 H 4.395948 1.915409 2.150409 H 2.662329 1.641171 2.387722 H 6.678917 1.435109 1.035624 H 7.415351 1.688951 0.552343 H 6.688253 3.055128 0.315812 N 1.435139 2.086687 3.022635 O 2.187418 2.037097 3.995299 C 0.882399 1.128629 1.886811 C 1.252359 1.391168 1.341582 H 0.880436 0.824497 2.928288 H 1.856524 1.237550 1.426659 H 1.073884 1.685579 2.381453 C 2.638058 1.737671 0.899909 H 2.844819 1.428858 0.120800 H 2.73 9910 2.830508 0.980956 O 3.561246 1.069852 1.791908 C 4.875222 1.414513 1.857382 O 5.637467 0.685975 2.448488 C 5.303441 2.721803 1.216570 H 5.074209 2.745322 0.146127 H 4.791604 3.571811 1.682295 H 6.378854 2.831145 1.358937 TS7E B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8073416700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9765554700 a.u Ru 0.062856 0.806937 0.139576 O 2.211299 2.433415 1.997658 O 0.393074 3.509566 2.336748 O 0.875632 2.662893 0.736221 N 0.700640 0.839688 2.428437 N 1.067291 1.838149 1.608891 C 0.246456 0.746254 1.459068 C 0.671868 2.098296 3.177274 C 1.86412 2 0.051337 2.409147 C 3.055519 0.619149 1.672268 C 4.231686 0.371292 1.568574 C 4.677403 0.775940 2.988883 C 3.497054 1.437098 3.730819 C 2.326053 0.432439 3.836262 C 3.044264 2.686364 2.947 590 C 2.592554 2.285531 1.520463 C 1.412550 1.305981 1.644928 C 3.771195 1.617420 0.785996 C 2.382942 2.076543 1.079067 C 2.549891 2.958439 0.005839 C 3.847811 3.214336 0.466636 C 1.384314 3.637337 0.687892 C 0.529967 0.450696 1.207967 C 1.318385 0.281187 2.435618 C 1.258495 0.858875 3.259226 C 2.460755 4.739902 1.521227 C 0.693872 2.664017 2.780674 C 3.062084 3.562159 2.280792 C 2.176613 1.350043 2.833146 C 3.507647 1.538212 1.744502 C 4.974069 2.640604 0.125863 C 1.999793 0.948175 4.433647 C 4.502143 3.268448 1.858374 C 2.930986 1.248165 4.007208 C 2.836211 0.104 710 4.802459 C 4.780249 1.818781 1.241340 C 3.382034 0.693643 2.995283 C 6.359682 2.885725 0.421772 H 0.612324 1.801261 2.248310 H 0.372801 1.503971 0.979098 H 0.767005 1.927379 4.253071 H 1.496655 2.750515 2.861211 H 2.729790 0.935371 0.674383 H 3.372750 1.518499 2.220585 H 5.065536 0.115742 1.044880 H 5.029181 0.106200 3.543323 H 5.521325 1.476388 2.932952 H 3.810580 1.722048 4.743875 H 1.486483 0.875957 4.388715 H 2.652948 0.457886 4.394030 H 2.221991 3.189036 3.475985 H 3.871232 3.408031 2.890517 H 2.274714 3.170699 0.968996 H 3.464403 1.341088 0.229823 H 4.604 151 2.327633 0.691093 H 3.977047 3.885111 1.313617 H 1.650829 4.662406 0.967526

PAGE 103

96 H 0.496975 3.671582 0.051819 H 1.098099 3.116531 1.610088 H 0.608530 1.679598 2.977027 H 2.459255 4.540582 0.4 43724 H 3.048035 5.646521 1.702216 H 1.430884 4.922860 1.842732 H 0.662998 3.722370 2.505020 H 1.437252 2.543742 3.577433 H 3.016136 3.777794 3.355958 H 1.923785 1.837114 5.052170 H 4.899011 2.384098 2.364785 H 5.149863 4.119811 2.096590 H 4.547857 3.091815 0.778008 H 3.596875 2.047059 4.309458 H 3.426784 0.044326 5.712906 H 5.645240 1.380440 1.734393 H 3.398077 1.320219 3.897384 H 4.223879 0.000934 3.076978 H 2.457937 0.109671 3.017731 H 6.685669 2.042860 1.044571 H 7.095140 2.996721 0.382627 H 6.393010 3.787210 1.041879 N 0.410648 3.692317 1.390604 O 0.806286 4.808005 1.057315 C 1.581821 0.185519 1.468459 C 1.833833 1.388421 0.754468 H 1.304505 0.268285 2.514025 H 2.105483 0.723231 1.193943 H 1.601498 2.291351 1.311882 C 2.977912 1.536469 0.217475 H 3.143804 0.621684 0.777591 H 2.792539 2.354450 0.921702 O 4.231772 1.751417 0.472499 C 4.643429 2.975407 0.916357 C 3.781788 4.191450 0.630690 H 3.586045 4.313195 0.440485 H 2.815867 4.13 3932 1.144403 H 4.320137 5.067632 0.993008 O 5.692647 3.033930 1.512389 TS8E B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.7999733700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9722216900 a.u Ru 0.236858 0.30 3130 0.776537 O 2.175211 2.294293 1.661421 O 0.239230 1.238149 3.888666 O 1.516122 0.120889 2.468257 N 0.432848 1.851804 1.622326 N 1.317129 0.595562 2.048250 C 0.414547 0.947281 1.063500 C 0.296100 1.978172 3.074662 C 1.596309 2.328472 0.860404 C 2.852056 1.474067 1.170465 C 4.034743 1.936263 0.295991 C 4.331948 3.421687 0.584565 C 3.082363 4.266989 0.262255 C 1.916640 3.808598 1.169403 C 2.708751 4.080899 1.225518 C 2.399912 2.587827 1.509243 C 1.198831 2.184062 0.628582 C 3.657925 1.754755 1.186433 C 2.642828 0.068792 1.854829 C 2.914856 1.290897 2.090834 C 4.21 0610 1.769301 1.848085 C 1.884950 2.248596 2.645222 C 0.154823 1.997345 0.183959 C 1.405790 2.698153 0.547546 C 1.612026 3.280795 1.808635 C 2.036306 2.555191 4.018481 C 1.063785 1.311702 3. 319392 C 2.959268 2.677593 2.809742 C 2.415514 2.866973 0.435582 C 3.697356 0.957116 1.530494 C 5.244930 0.935982 1.424549 C 2.769493 3.991648 2.107647 C 4.202936 1.796813 2.940564 C 3.578114 3.587949 0.136940 C 3.751966 4.144688 1.130379 C 4.972355 0.433285 1.311463 C 3.499409 2.458176 1.455359 C 6.606698 1.482093 1.072431 H 0.393872 2.911640 0.808634 H 0.024032 1.872763 0.88341 1 H 0.321020 3.024250 3.392130 H 1.110888 1.447566 3.585981 H 2.633127 0.413235 0.983491 H 3.111412 1.563688 2.236299 H 4.917793 1.328957 0.536205 H 4.621257 3.559062 1.636869 H 5.180143 3. 758534 0.026165 H 3.291249 5.326175 0.463285 H 1.022503 4.420964 0.990384 H 2.201848 3.942937 2.224015 H 1.838468 4.703650 1.476539 H 3.539836 4.424277 1.857824 H 2.141873 2.452960 2.564509 H 3.473326 0.701868 1.416687 H 4.491030 2.081529 1.824088 H 4.409796 2.828598 1.997508 H 2.252721 2.692680 3.578608 H 0.935205 1.753793 2.855805 H 1.689758 3.075391 1.953278 H 0.855475 3.158440 2.575178 H 1.692514 1.520781 4.134354 H 2.566072 2.844166 4.932798 H 1.160653 3.201498 3.905069 H 1.053546 0.607104 4.156725 H 1.852638 2.048481 3.509178

PAGE 104

97 H 3.250948 3.728824 2.692503 H 2.902240 4.416504 3.097516 H 4.824028 1.835681 2.041309 H 4.811153 2.122806 3.792337 H 3.912203 0.753741 3.105060 H 4.357675 3.711748 0.878587 H 4.663307 4.695279 1.347481 H 5.778929 1.11 2233 1.040399 H 3.659411 2.924144 2.437137 H 4.225337 2.913342 0.773457 H 2.497145 2.739269 1.120392 H 6.712735 1.543661 0.018159 H 7.409603 0.836314 1.446342 H 6.756646 2.485993 1.482133 N 1.352119 0.737488 3.610870 O 2.319793 0.791766 4.365195 C 0.974045 1.850924 0.977134 C 1.223792 0.495440 1.883345 H 0.983962 2.149225 2.019294 H 1.937898 1.673521 0.516354 H 1.028563 0.173890 2.913901 C 2.614828 1.010473 1.689026 H 2.821198 1.297360 0.661661 H 2.726196 1.890144 2.341656 O 3.536892 0.033025 2.078153 C 4.854109 0.220011 2.302914 O 5.620015 0.711777 2.379857 C 5.282568 1.664130 2.490222 H 5.051375 2.276079 1.612014 H 4.773790 2.114541 3.350266 H 6.358593 1.676336 2.665550 4E B3LYP/SDD/6 31G(d) SCF energy in gas phase: 1647.0297834600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1646.4066488000 a.u Ru 0.437631 0.148582 0.958097 O 0.418626 1.937681 1.834177 O 0.811874 0.677634 3.114160 N 1.074963 0.041059 1.843154 N 1.076378 0.509762 1.711092 C 0.028452 0.209526 0.979635 C 0.756536 0.504251 3.197708 C 2.407475 0.082387 1.218300 C 2.856121 1.547612 0.963147 C 4.180262 1.567842 0.174677 C 5.261841 0.833482 0.993011 C 4.817570 0.622575 1.243351 C 3.4943 57 0.628327 2.048575 C 4.622010 1.327347 0.117863 C 3.525572 0.597485 0.937741 C 2.216823 0.661002 0.126311 C 3.971507 0.859155 1.179257 C 2.349559 0.957050 1.209315 C 2.496031 2.320402 0.870533 C 3.736598 2.761901 0.408750 C 1.353730 3.300685 1.001380 C 0.784084 0.532047 3.160926 C 3.441684 0.076203 1.139659 C 4.833034 1.899923 0.287451 C 4.667076 0.569843 0.672565 C 3.3555 69 1.378940 1.539317 C 6.153178 2.400511 0.249694 H 2.041407 1.712926 0.131240 H 1.145744 0.176981 3.959483 H 1.178155 1.502686 3.382744 H 2.074644 2.079852 0.400289 H 2.976540 2.080224 1.91 7318 H 4.485657 2.609003 0.007488 H 5.430361 1.350491 1.948298 H 6.217060 0.845623 0.451264 H 5.587285 1.148135 1.823318 H 3.178956 1.657945 2.263784 H 3.647804 0.123601 3.014335 H 4.339470 2.377933 0.035246 H 5.571928 1.329781 0.670697 H 3.386835 1.104577 1.900507 H 3.220557 1.391904 1.777911 H 4.904414 0.875744 1.758931 H 3.850552 3.809576 0.138885 H 0.844399 3.215661 1.968569 H 0.606991 3.144058 0.216140 H 1.719929 4.327339 0.906931 H 1.210366 1.425548 3.625203 H 1.221440 0.347096 3.651752 H 5.512962 0.111994 0.611712 H 4.258632 1.682086 2.080359 H 3.278732 2.02 2107 0.654870 H 2.495015 1.585392 2.181122 H 6.132402 2.462222 1.345533 H 6.977353 1.734776 0.025932 H 6.384798 3.403620 0.125768 N 0.114726 1.748103 3.019149 O 0.043797 2.534348 3.921041 C 0.256436 1.494357 1.304074 H 0.299828 1.748626 2.376567 C 0.660681 2.626167 0.417512 H 0.931418 2.291934 0.586562 H 0.217740 3.287246 0.330635 O 1.764507 3.338655 1.011283 C 2.081502 4.616297 0.650338 O 3.047596 5.135278 1.152658 C 1.189756 5.317361 0.359306 H 1.071132 4.732666 1.277818 H 0.189235 5.491598 0.053564 H 1.644763 6.279391 0.596155 TS30 B3LYP/SDD/6 31G( d) SCF energy in gas phase: 2149.8307240800 a.u.

PAGE 105

98 M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9947634800 a.u Ru 0.490638 0.393296 0.853660 O 0.833441 1.377602 3.018976 O 0.818025 0.769987 2.712787 N 1.628735 2.05 3740 1.221034 N 0.535385 2.308339 1.460616 C 0.429472 1.704184 0.694397 C 1.529809 2.754434 2.501350 C 2.847375 1.446256 0.680741 C 3.255957 0.186211 1.483318 C 4.466881 0.489066 0.809547 C 5.651510 0.497598 0.778895 C 5.246804 1.756520 0.015310 C 4.041241 2.432172 0.680811 C 4.875594 1.346987 1.457498 C 3.673597 0.365436 1.432232 C 2.489827 1.106766 0.780837 C 4.078700 0.888206 0.628894 C 1.899183 2.580844 1.096234 C 2.935174 1.962263 1.820844 C 4.258910 2.279688 1.498259 C 2.646401 0.981803 2.934129 C 0.059002 3.186997 2.495463 C 2.183623 3.542032 0.103662 C 4.576375 3.199068 0.494377 C 3.523734 3.826313 0.179594 C 1.090219 4.235821 0.676950 C 6.013604 3.492870 0.134393 H 2.368855 2.064972 1.304548 H 2.220799 3.600159 2.555982 H 1.754744 2.073349 3.334199 H 2.409351 0.507763 1.524223 H 3.506106 0.466446 2.517295 H 4.745173 1.384506 1.381288 H 5.945602 0.770927 1.802568 H 6.525373 0.023971 0.311287 H 6.085321 2.465178 0.036384 H 3.75 7201 3.352181 0.152893 H 4.322777 2.713112 1.707065 H 4.622162 2.233693 2.053459 H 5.743063 0.873877 1.939555 H 3.423939 0.078118 2.459259 H 3.256375 1.611640 0.606265 H 4.928402 1.384280 1. 118834 H 5.062475 1.794743 2.048220 H 3.577768 0.564339 3.328267 H 2.120294 1.458854 3.771084 H 2.018980 0.149951 2.599019 H 0.436799 3.043545 3.459196 H 0.060981 4.238969 2.205265 H 3.748853 4.559028 0.951680 H 0.299458 4.629476 0.028829 H 1.501532 5.073803 1.247455 H 0.608646 3.553082 1.387081 H 6.364117 2.818642 0.657944 H 6.133635 4.517466 0.233314 H 6.678706 3.358333 0.993972 C 0.032891 1.014387 0.384403 H 0.413149 0.738997 1.366405 C 0.278342 2.464078 0.357359 C 0.075364 3.280881 1.472985 C 0.951817 3.084732 0.712799 C 0.264623 4.641027 1.488635 C 1.27272 6 4.439323 0.701469 H 1.224470 2.482347 1.570171 C 0.930780 5.214544 0.405715 H 0.011011 5.264976 2.336625 H 1.794508 4.880223 1.545666 H 1.181317 6.271677 0.437312 O 0.770270 2.669762 2.480 772 C 1.076521 3.371827 3.702822 H 1.428735 4.380417 3.452124 C 0.156700 3.449162 4.603549 H 0.077157 3.997893 5.522845 H 0.483999 2.440106 4.878233 H 0.989445 3.954699 4.106254 C 2.225383 2.606940 4.350279 H 2.541772 3.111335 5.269560 H 3.082322 2.549995 3.672192 H 1.915539 1.587871 4.605346 N 0.953229 0.222547 3.539956 O 1.178650 0.035986 4.722755 C 1.489409 0.611306 1.549485 C 1.680753 0.546428 0.693418 H 1.969198 1.536965 1.258085 H 1.519587 0.424448 2.622312 H 2.261910 0.347184 0.203621 C 2.054816 1.839690 1.391518 H 2.051863 2.689247 0.703034 H 1.355679 2.035 784 2.208336 O 3.395646 1.651063 1.893222 C 3.955825 2.529501 2.771212 O 5.109533 2.369680 3.090474 C 3.084795 3.646828 3.314963 H 2.629546 4.240259 2.514906 H 2.269781 3.242739 3.926887 H 3.709639 4.289589 3.935528 19 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8355385200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2149.0033501900 a.u Ru 0.313207 0.211518 0.968389 O 0.337999 0.674840 3.484431 O 0. 617798 1.272352 2.551866 N 1.377974 2.334751 0.657586 N 0.752016 2.329550 1.169641 C 0.191950 1.745843 0.366702 C 1.334438 3.197916 1.837017

PAGE 106

99 C 2.584655 1.803479 0.022234 C 3.222874 0.669307 0.867863 C 4.408266 0.049848 0.101508 C 5.464319 1.141224 0.165793 C 4.832674 2.273775 1.001679 C 3.651946 2.894955 0.220015 C 4.331064 1.694939 2.341666 C 3.262354 0.599448 2.079604 C 2.09278 6 1.270850 1.339723 C 3.894947 0.526050 1.234512 C 2.175884 2.357694 0.965993 C 3.017013 1.751738 1.918150 C 4.401741 1.837351 1.735394 C 2.463642 1.035159 3.128445 C 0.174728 3.436532 1.970 261 C 2.713398 3.086003 0.116208 C 4.966640 2.515937 0.652065 C 4.103962 3.143012 0.252687 C 1.830969 3.773203 1.133840 C 6.463241 2.555404 0.452898 H 1.728163 2.119829 1.932234 H 1.899680 4.121540 1.685942 H 1.747583 2.679854 2.714303 H 2.469397 0.097141 1.085293 H 3.563698 1.074595 1.831996 H 4.848806 0.752744 0.707396 H 5.848011 1.538718 0.784829 H 6.321778 0.714109 0.702779 H 5.580768 3.054397 1.192280 H 3.209257 3.724867 0.786761 H 4.014857 3.302898 0.735282 H 3.905494 2.490979 2.966950 H 5.175247 1.266145 2.899689 H 2.924667 0.200623 3.039695 H 3.160873 1.319 687 1.049601 H 4.726135 0.983489 1.788610 H 5.054967 1.359151 2.461982 H 3.269780 0.552900 3.689471 H 1.958689 1.727823 3.814645 H 1.731822 0.267773 2.859768 H 0.529394 3.396086 3.003186 H 0.476889 4.401448 1.542608 H 4.522929 3.693059 1.092572 H 1.077135 4.415225 0.663634 H 2.431852 4.399295 1.799856 H 1.290659 3.047683 1.753023 H 6.796935 1.714061 0.168273 H 6.776768 3.476337 0.050114 H 6.997276 2.488460 1.406614 C 0.212285 1.063833 0.506486 H 0.385960 0.594332 1.468082 C 0.475997 2.375652 0.733856 C 0.809264 2.749610 2.068093 C 0.856409 3.259577 0.291733 C 1.473 547 3.955391 2.325324 C 1.513214 4.462808 0.033706 H 0.656522 2.985195 1.319514 C 1.819995 4.810727 1.278429 H 1.727833 4.239499 3.339101 H 1.789596 5.113419 0.858416 H 2.334047 5.742340 1.499727 O 0.431091 1.876499 3.059096 C 0.787014 2.115693 4.432771 H 0.621763 3.175906 4.664009 C 2.248084 1.740822 4.688399 H 2.515620 1.936490 5.733100 H 2.400739 0.674394 4.487277 H 2.92921 8 2.309192 4.048736 C 0.179805 1.283878 5.269117 H 0.009433 1.443583 6.336172 H 1.215686 1.563082 5.053976 H 0.056556 0.216820 5.053459 N 0.521007 0.563989 3.645389 O 0.612633 1.104290 4.736 630 C 1.645138 0.102836 1.424918 C 1.627096 0.990687 0.313560 H 2.306094 0.934572 1.208018 H 1.814214 0.293126 2.428135 H 2.331602 0.652217 0.450001 C 2.102341 2.335910 0.856801 H 2.014440 3.118427 0.095531 H 1.522288 2.624325 1.736699 O 3.489926 2.156333 1.199558 C 4.190737 3.109984 1.873487 O 5.368966 2.930335 2.068724 C 3.439759 4.337054 2.355091 H 2.919151 4.845339 1.536330 H 2.686810 4.064912 3.103929 H 4.160688 5.018656 2.807049 TS31 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 2149.8051696200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9710650000 a.u Ru 0.242084 0.060213 0.813477 O 0.839128 2.663652 2.818950 O 0.913424 1.769284 1.817966 N 1.274210 2.619164 0.024107 N 0.753627 2.623302 0.809921 C 0.135100 1.887111 0.067301 C 1.287472 3.789604 0.854643 C 2.441367 2.015 663 0.675001 C 3.294668 1.222201 0.348402 C 4.450263 0.503313 0.374012 C 5.334227 1.549906 1.083549 C 4.483518 2.332594 2.104803 C 3.342730 3.065940 1.359503 C 3.901320 1.346348 3.141183 C 3.002846 0.299884 2.432773

PAGE 107

100 C 1.850498 1.062912 1.746071 C 3.857609 0.474063 1.407863 C 2.176631 2.426752 0.853816 C 2.765986 1.898706 2.017888 C 4.140558 1.632003 2.007657 C 1.955898 1.624499 3.264746 C 0.209479 3.955667 1.151947 C 2.972767 2.802953 0.249683 C 4.937124 1.888545 0.888429 C 4.338644 2.511437 0.212294 C 2.399458 3.532200 1.446473 C 6.382997 1.461669 0.834183 H 1.365 688 1.699517 2.500360 H 1.722328 4.662177 0.360569 H 1.867156 3.585877 1.766793 H 2.658868 0.490120 0.868235 H 3.688288 1.905752 1.116179 H 5.049935 0.047796 0.363089 H 5.776056 2.238448 0.3 48413 H 6.168098 1.050888 1.594874 H 5.109913 3.078219 2.612009 H 2.744477 3.661248 2.062452 H 3.774866 3.760973 0.623256 H 3.321284 1.891624 3.898436 H 4.723472 0.844433 3.670938 H 2.596532 0.404199 3.164153 H 3.245077 1.235943 0.913067 H 4.667358 1.006195 1.925662 H 4.593156 1.184940 2.890132 H 1.788649 2.548046 3.836379 H 0.971546 1.207358 3.037445 H 2.481190 0.927229 3.924575 H 0.418143 4.203970 2.196225 H 0.668628 4.724363 0.516814 H 4.949617 2.756141 1.078514 H 2.324370 4.610212 1.247913 H 3.049094 3.412951 2.319014 H 1.401294 3.179684 1.719207 H 6.471164 0.5 43949 0.237742 H 7.011829 2.224466 0.360965 H 6.782818 1.259472 1.833194 C 0.444905 1.190061 1.009083 H 0.218955 0.426566 1.744246 C 0.319768 2.437270 1.225056 C 1.250267 2.473835 2.300931 C 0.164116 3.603292 0.456921 C 1.954928 3.648596 2.587034 C 0.866132 4.771624 0.741869 H 0.489282 3.586355 0.405269 C 1.757918 4.792176 1.811626 H 2.664432 3.682131 3.404448 H 0.727039 5.650830 0.120495 H 2.316846 5.694314 2.045153 O 1.387191 1.313548 3.018028 C 2.197802 1.267129 4.209035 H 2.073406 2.212486 4.752273 C 3.669804 1.048568 3.856074 H 4.280946 1.036610 4.765857 H 3.795363 0.088216 3.344053 H 4.050056 1.835538 3.198591 C 1.628095 0.135274 5.058272 H 2.185748 0.047170 5.996923 H 0.575925 0.321005 5.294928 H 1.700900 0.818980 4.524390 C 1.681754 1.024027 0.373918 C 1.319799 0.180090 1.778580 H 2.248854 0.149052 0.663637 H 1.487451 0.581575 2.548793 H 2.112258 0.919213 1.653760 C 2.550058 2.101345 0.223676 H 2.698329 2.902956 0.516551 H 2.117 030 2.524664 1.129292 O 3.820152 1.476071 0.490360 C 4.732838 2.016217 1.340764 O 5.804067 1.463036 1.452486 C 4.351115 3.269685 2.100619 H 4.084822 4.083340 1.416316 H 3.486523 3.095751 2.7 50806 H 5.206523 3.572541 2.704946 N 0.405909 2.492868 2.771116 O 1.174195 3.004732 3.582547 20 B3LYP/SDD/6 31G(d) SCF energy in gas phase: 1379.8452126200 a.u. M06/SDD/6 311++ G(d,p) SCF energy in solution: 1379.282105970 a.u Ru 0.266275 0.956504 0.428114 O 1.176969 2.705296 0.224892 O 0.959529 2.932975 0.147552 N 0.854277 1.767955 0.344293 N 1.332892 1.604045 0.424816 C 0.189925 0.948219 0.120227 C 0.466485 3.006909 1.026307 C 2.200818 1.194726 0.205418 C 2.666147 0.580315 1.551241 C 4.020450 0.130367 1.365090 C 5.063191 0.893526 0.871958 C 4.596369 1.498524 0.468527 C 3.247288 2.228042 0.257763 C 4.437689 0.364102 1.505597 C 3.376335 0.656239 1.015742 C 2.029853 0.086809 0.869779 C 3.852326 1.255858 0.324613 C 2.666316 1.101839 0.256069 C 3.231604 0.300448 1.266074 C 4.544359 0.148 525 1.098235 C 2.447429 0.100710 2.492787 C 1.065671 3.001850 0.829693 C 3.397496 1.446022 0.895877

PAGE 108

101 C 5.298677 0.171258 0.035275 C 4.707482 0.970611 1.017352 C 2.803023 2.302746 1.990239 C 6.704740 0.356527 0.201088 H 1.846809 0.610770 1.823836 H 0.946355 3.880130 0.576623 H 0.746020 2.969647 2.088223 H 1.910133 0.136966 1.905175 H 2.746787 1.364622 2.318431 H 4.342658 0.553063 2.325970 H 5.202565 1.687072 1.620280 H 6.037336 0.403348 0.741784 H 5.339483 2.224354 0.824192 H 2.913147 2.696833 1.192892 H 3.375549 3.030060 0.485708 H 4.139596 0.779108 2.478048 H 5.406 795 0.133595 1.653913 H 3.270634 1.458204 1.756908 H 3.135371 2.003094 0.683520 H 4.809700 1.776027 0.181785 H 4.986611 0.769676 1.874233 H 1.857002 0.729077 2.896371 H 1.752464 0.915665 2.2 55152 H 3.117692 0.457434 3.280679 H 1.616629 3.250206 1.741062 H 1.377527 3.695026 0.039235 H 5.277245 1.229234 1.907542 H 2.821243 3.370277 1.731434 H 3.371064 2.189187 2.918526 H 1.762198 2.032000 2.195111 H 6.695924 1.402203 0.535168 H 7.265558 0.220944 0.943116 H 7.258532 0.324642 0.743914 C 0.439477 0.735258 2.076971 H 0.039582 0.069815 2.857573 H 1.324412 1.319739 2.373009 N 0.178286 3.491941 0.222344 O 0.223504 4.660579 0.533777 21 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1379.8544798500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1379.2864030800 a.u Ru 0.291827 0.893741 0.538281 O 0.808423 3.104984 0.727755 O 0.422809 2.328597 0.888482 N 0.785838 1.768970 0.345609 N 1.394564 1.510443 0.450654 C 0.234703 0.902630 0.091484 C 0.360181 2.904977 1.165312 C 2.143007 1.218 801 0.226826 C 2.564676 0.476670 1.523121 C 3.928898 0.211265 1.317435 C 4.984031 0.858210 0.965848 C 4.564542 1.591208 0.325110 C 3.202225 2.290796 0.098547 C 4.457287 0.564572 1.475458 C 3.387811 0.505389 1.129888 C 2.041257 0.221905 0.959555 C 3.811510 1.229842 0.164679 C 2.721706 0.998287 0.261160 C 3.286146 0.174295 1.254285 C 4.588001 0.297645 1.061912 C 2.521483 0.206562 2.500071 C 1.161912 2.890718 0.925907 C 3.457675 1.370140 0.879767 C 5.336208 0.028158 0.073837 C 4.755694 0.869446 1.026693 C 2.896747 2.307487 1.925580 C 6.726933 0.528923 0.270695 H 1.861 900 0.821111 1.857067 H 0.828930 3.838402 0.842347 H 0.606145 2.742758 2.225315 H 1.800507 0.269809 1.788551 H 2.617528 1.184785 2.362892 H 4.217916 0.726660 2.242668 H 5.089769 1.573730 1.7 93616 H 5.965191 0.385159 0.825680 H 5.315439 2.351047 0.578052 H 2.899209 2.845326 0.996523 H 3.293454 3.018015 0.722604 H 4.191824 1.071545 2.413013 H 5.434909 0.087872 1.634432 H 3.313634 1.229785 1.950183 H 3.083903 2.012184 0.416598 H 4.775497 1.734435 0.012993 H 5.028628 0.937186 1.823866 H 1.976708 0.645606 2.921456 H 1.788062 0.992264 2.288560 H 3.203754 0.585424 3.267406 H 1.742938 3.090396 1.830516 H 1.458220 3.616032 0.157259 H 5.326160 1.146382 1.911106 H 3.063178 3.358758 1.652641 H 3.386592 2.147579 2.891253 H 1.819972 2.174168 2.065052 H 6.690633 1.5 31163 0.717709 H 7.323151 0.104205 0.936107 H 7.260910 0.619388 0.681576 C 0.524768 0.785397 2.150454 H 0.371255 1.623825 2.847088 H 1.232875 0.022026 2.487563 N 0.145688 3.377025 0.327427 O 0.036565 4.482732 0.801481 TS32 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2149.8273869500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9932216200 a.u Ru 0.671533 0.710888 0.838736

PAGE 109

102 O 0.284335 3.477742 0.973179 O 1.155736 2.522759 2.315285 O 1.466027 0.453528 2.891641 N 1.265135 1.560228 1.864814 N 0.919630 1.622585 1.792678 C 0.201817 1.348363 1.047186 C 0.904137 1.795068 3.261875 C 2.612053 1.237357 1.389073 C 3.007582 0.214033 1.755943 C 4.371126 0.554418 1.122712 C 5.440594 0.412748 1.668935 C 5.048667 1.862547 1.316327 C 3.683911 2.194567 1.965823 C 4.961156 2.001148 0.219453 C 3.8 74373 1.041621 0.773019 C 2.532569 1.450617 0.134402 C 4.260932 0.407450 0.409213 C 2.257448 1.851271 1.329853 C 3.282057 0.987190 1.766626 C 4.585510 1.212723 1.313498 C 3.003163 0.158661 2 .713860 C 0.222019 1.115940 0.367439 C 0.728594 2.404611 0.889914 C 1.473893 2.514007 2.080488 C 1.732172 4.235685 2.682443 C 0.572844 2.169299 3.125217 C 0.505799 4.597703 1.851317 C 0.475697 3.604130 0.160155 C 2.553663 2.978774 0.538187 C 4.898925 2.273590 0.456706 C 1.955280 3.736189 2.541009 C 0.729178 4.861491 2.713489 C 0.977162 4.829891 0.616831 C 1.708330 4.893182 1.803275 C 3.873707 3.157239 0.106854 C 1.486452 3.969340 0.132918 C 6.295644 2.430436 0.094233 H 2.399244 2.529109 0.291802 H 0.371605 1.285942 0.530945 H 1.505616 2.591545 3.707443 H 1.04509 6 0.882212 3.858667 H 2.237686 0.903168 1.393384 H 3.061161 0.321657 2.849612 H 4.641434 1.587762 1.378489 H 5.535238 0.298150 2.758517 H 6.421748 0.175152 1.236108 H 5.804898 2.555533 1.708 261 H 3.399567 3.234071 1.754824 H 3.764508 2.088876 3.058343 H 4.723002 3.036415 0.496967 H 5.938256 1.766126 0.665219 H 3.825815 1.143967 1.862167 H 3.516816 1.109412 0.801237 H 5.221958 0.663345 0.877058 H 5.376726 0.536475 1.631546 H 2.925594 0.188971 3.753114 H 2.064959 0.670082 2.476119 H 3.815080 0.892510 2.686815 H 1.676076 1.615522 2.650456 H 1.544075 3.330237 3.269906 H 1.976454 5.050309 3.372415 H 2.598067 4.056716 2.037112 H 1.203314 1.734326 3.904170 H 0.724246 3.257236 3.129173 H 0.742285 5.482660 1.246294 H 2.524249 3.780819 3.464790 H 1.612977 5.059 634 2.100402 H 0.562167 5.727622 3.363748 H 0.939484 3.990897 3.344779 H 0.799198 5.742081 0.060440 H 2.083598 5.854593 2.143953 H 4.102669 4.009466 0.529107 H 0.891774 4.302532 0.991498 H 1.940015 4.854826 0.322025 H 0.785570 3.540090 0.591922 H 6.470456 1.699355 0.894166 H 6.453286 3.429717 0.511989 H 7.054774 2.258893 0.677667 N 1.563094 1.708420 3.208853 O 2.014772 2.061047 4.282848 C 1.212917 0.977123 1.840488 C 1.221239 0.453508 1.688119 H 0.980226 1.364196 2.828445 H 1.964170 1.546040 1.306355 H 0.867798 1.017034 2.548227 C 2.398024 1.095560 0.982595 H 2.260 481 2.177311 0.899909 H 2.537057 0.667109 0.011138 O 3.569885 0.794732 1.777231 C 4.786483 1.309685 1.463615 O 5.769925 0.861901 2.006334 C 4.840349 2.455755 0.468584 H 4.279359 3.320674 0.841353 H 4.407869 2.174887 0.497591 H 5.884687 2.737415 0.331335 TS35 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2149.8116579400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9821288700 a.u Ru 0.859473 0.444452 0.841103 O 0.641752 1.464676 4.037999 O 1.828238 0.192089 2.685522 N 1.575768 2.038812 1.462211 N 0.610061 2.126101 1.472073 C 0.469800 1.606926 0.797156 C 1.285741 2.694017 2.737006 C 2.89229 9 1.526260 1.084238 C 3.253309 0.269148 1.917648

PAGE 110

103 C 4.586402 0.323945 1.423143 C 5.699731 0.732063 1.577298 C 5.341108 1.982171 0.747169 C 4.011463 2.578111 1.267672 C 5.200005 1.580035 0.737 081 C 4.072184 0.527174 0.897646 C 2.761986 1.167600 0.403139 C 4.433642 0.717205 0.059882 C 1.972215 2.257677 1.036825 C 2.967758 1.519488 1.705333 C 4.302112 1.690944 1.319199 C 2.621137 0.565108 2.825438 C 0.193105 3.037820 2.563030 C 2.318969 3.215568 0.062117 C 4.671976 2.576845 0.301495 C 3.665197 3.340372 0.297947 C 1.284966 4.116486 0.576756 C 6.106747 2.682341 0.155978 H 2.609953 2.112702 0.970006 H 1.913640 3.575433 2.890100 H 1.452463 2.002405 3.575233 H 2.446752 0.467340 1.817818 H 3.329754 0.536287 2.981795 H 4.831912 1.211064 2.022320 H 5.824769 1.00 1060 2.636149 H 6.659438 0.320454 1.237190 H 6.132241 2.735937 0.854491 H 3.753635 3.490317 0.712855 H 4.124554 2.856918 2.326065 H 4.980255 2.463141 1.352358 H 6.153329 1.169557 1.099270 H 3.967678 0.252601 1.949769 H 3.658903 1.486064 0.166343 H 5.372210 1.153451 0.429313 H 5.073431 1.116729 1.828816 H 3.507415 0.007845 3.143929 H 2.237050 1.094923 3.706650 H 1.852023 0.155678 2.529436 H 0.787997 2.865347 3.463438 H 0.338703 4.080696 2.252405 H 3.933535 4.057175 1.070691 H 0.899845 4.853788 0.139813 H 1.723184 4.671799 1.410945 H 0.424790 3.557972 0.957642 H 6.30 9453 1.944093 0.942481 H 6.324812 3.673442 0.567091 H 6.805200 2.491773 0.666272 C 0.112976 1.121855 0.028246 H 0.561351 0.995310 0.818121 C 0.487706 2.532449 0.214795 C 0.052549 3.526024 0. 657323 C 1.396831 2.953951 1.206869 C 0.343353 4.863405 0.528495 C 1.772217 4.285903 1.340343 H 1.788257 2.207230 1.886507 C 1.247580 5.237156 0.466075 H 0.049264 5.624561 1.191100 H 2.468213 4.576672 2.121070 H 1.536481 6.281529 0.551424 O 0.971193 3.100277 1.580540 C 1.481076 4.004527 2.582444 H 1.719167 4.962847 2.104371 C 0.454510 4.208380 3.697005 H 0.841614 4.905702 4.448548 H 0.241428 3.253203 4.189794 H 0.485955 4.610409 3.309579 C 2.778178 3.385080 3.090088 H 3.249034 4.047617 3.824125 H 3.480298 3.228092 2.265170 H 2.584518 2.420624 3.570905 C 0.8925 88 0.871064 2.004719 C 1.171168 0.491468 1.662107 H 0.521929 1.074551 3.008805 H 1.558846 1.631023 1.613471 H 0.834892 1.244060 2.370093 C 2.453099 0.835266 0.936164 H 2.483147 1.900816 0.69 3699 H 2.567435 0.251027 0.021830 O 3.538086 0.488221 1.830804 C 4.821808 0.817788 1.541632 O 5.715366 0.312281 2.181795 C 5.068832 1.837439 0.443611 H 4.593735 2.795060 0.686008 H 4.664301 1.500227 0.516702 H 6.145553 1.983451 0.353035 N 1.250439 0.399796 3.861250 O 1.373612 0.475057 4.717772 22 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2149.8371509900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2149.0085626900 a.u Ru 0.505679 0.686398 0.866081 O 0.727116 3.051720 1.327820 O 0.838060 2.445658 2.645121 O 1.179384 0.313631 2.910232 N 1.138952 1.601836 1.801432 N 1.023220 1.297916 1.902093 C 0.059440 1.236306 1.060346 C 0.872065 1.694680 3.235072 C 2.462539 1.489840 1.192843 C 3.063913 0.075273 1.400120 C 4.389426 0.049319 0.623751 C 5.382575 1.007844 1.147434 C 4.786027 2.417 063 0.950005 C 3.461905 2.534357 1.741163 C 4.524537 2.647669 0.552921 C 3.519172 1.590899 1.086007 C 2.210622 1.777935 0.297650

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104 C 4.113336 0.181989 0.876041 C 2.416986 1.357890 1.562966 C 3.270609 0.331227 2.010668 C 4.634033 0.413730 1.702938 C 2.752303 0.838550 2.816250 C 0.126235 1.217957 0.541839 C 0.694953 2.396872 0.952933 C 1.084301 2.648194 2.279552 C 0.005675 3.698235 3.489292 C 0.652246 1.826376 3.236610 C 1.041691 3.957358 2.399943 C 1.118155 3.326403 0.037969 C 2.935203 2.488045 0.896404 C 5.167998 1.484139 0.978533 C 1.841833 3.765656 2.631637 C 2.472099 3.738881 2.897292 C 1.877461 4.447590 0.314996 C 2.234637 4.667437 1.647447 C 4.303022 2.518663 0.606447 C 2.050595 3.641260 0.481362 C 6.624202 1.505136 0.579954 H 1.862818 2.813175 0.399632 H 0.558452 1.389839 0.442185 H 1.374935 2.553289 3.687781 H 1.206923 0.784798 3.754209 H 2.348414 0.683087 1.061823 H 3.235042 0.097658 2.473122 H 4.803578 1.054803 0.774838 H 5.59 8407 0.831769 2.211010 H 6.337028 0.929305 0.610022 H 5.489660 3.172406 1.323684 H 3.037941 3.541947 1.635917 H 3.653872 2.365753 2.811359 H 4.131041 3.658307 0.723942 H 5.469485 2.572916 1. 109058 H 3.354604 1.770565 2.151191 H 3.426693 0.581919 1.260875 H 5.046669 0.086668 1.447520 H 5.295559 0.383108 2.037946 H 2.616886 0.570486 3.873116 H 1.785638 1.194799 2.448886 H 3.460869 1.672764 2.790141 H 0.809724 1.938845 3.050803 H 0.076807 2.665300 3.848207 H 0.171010 4.369620 4.338909 H 1.006661 3.863285 3.107695 H 1.135564 1.253340 4.031483 H 0.974524 2.872696 3.32339 7 H 0.920040 4.987169 2.039685 H 2.123605 3.920628 3.668971 H 3.202942 3.870727 2.094556 H 2.710353 4.448204 3.698242 H 2.580768 2.722801 3.292651 H 2.200415 5.156768 0.437578 H 2.824886 5. 543608 1.902375 H 4.702573 3.375435 0.068648 H 1.444833 4.012266 1.316510 H 2.656116 4.474332 0.112817 H 1.354641 3.352945 0.314291 H 6.763756 0.986117 0.377254 H 6.992023 2.529000 0.456477 H 7.252717 1.003388 1.323909 N 1.178418 1.511337 3.428084 O 1.500397 1.683099 4.591833 C 1.368945 0.819883 1.629945 C 1.272495 0.730705 1.559074 H 1.378325 1.205622 2.649161 H 2.174342 1.240179 1.036481 H 1.032542 1.107469 2.553447 C 2.581749 1.365388 1.087687 H 2.493537 2.455824 1.159325 H 2.793795 1.087001 0.053127 O 3.646919 0.886495 1.929316 C 4.922072 1.327546 1.772026 O 5.817481 0.742809 2.336397 C 5.147000 2.561206 0.916214 H 4.593377 3.420339 1.311616 H 4.814694 2.400394 0.114782 H 6.213624 2.787278 0.920762 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2149.827250 2300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2149.0021283400 a.u Ru 0.503866 0.192523 0.997549 O 0.968582 1.871964 2.590919 O 0.049797 2.182983 3.627263 O 1.526972 0.985560 2.500820 N 1.066487 2.408 869 0.743457 N 1.073473 2.095054 1.073647 C 0.009317 1.646098 0.355820 C 0.800777 3.245850 1.911758 C 2.395000 2.093256 0.223920 C 3.129637 1.076827 1.139067 C 4.474156 0.671046 0.504390 C 5.347625 1.929331 0.322515 C 4.617562 2.937586 0.589665 C 3.280580 3.350824 0.066901 C 4.348892 2.282021 1.960149 C 3.469314 1.015742 1.783636 C 2.139236 1.464928 1.156289 C 4.203843 0.017252 0.865247 C 2.469043 1.936158 0.773311 C 3.292707 1.270689 1.700536 C 4.664043 1.176562 1.430622 C 2.732120 0.671720 2.970576 C 0.152417 1.347595 0.146692 C 0.682870 2.567301 0.341291 C 0.94 8035 3.503245 0.672610

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105 C 0.422736 1.255775 4.814168 C 0.729171 3.267434 1.913964 C 1.378283 2.078629 3.955628 C 1.237035 2.814744 1.627684 C 3.023362 2.567258 0.361192 C 5.233780 1.729230 0. 279614 C 1.711445 4.645260 0.437625 C 2.837736 1.665240 4.154455 C 2.004116 3.961620 1.862485 C 2.236916 4.873913 0.831586 C 4.395586 2.433728 0.591644 C 2.179418 3.389241 1.309716 C 6.699248 1.547366 0.034323 H 1.657380 2.216423 1.811498 H 0.558654 1.013156 1.100709 H 1.240506 4.241085 1.807550 H 1.207300 2.782441 2.822233 H 2.493128 0.195042 1.287485 H 3.296414 1.528329 2.12849 0 H 4.984190 0.041266 1.166402 H 5.564186 2.387639 1.298398 H 6.313393 1.655875 0.122840 H 5.238398 3.833575 0.720643 H 2.759650 4.094188 0.551628 H 3.477283 3.813986 1.045173 H 3.854028 2. 996012 2.633018 H 5.301254 2.006260 2.433862 H 3.281495 0.550820 2.752563 H 3.603627 0.892653 0.748016 H 5.151983 0.284251 1.330631 H 5.302156 0.655250 2.141735 H 2.540979 1.442543 3.729512 H 1.784215 0.153648 2.796619 H 3.439838 0.038706 3.409482 H 0.560854 3.327713 1.669863 H 0.503269 0.191388 4.566028 H 0.662977 1.379946 5.875738 H 0.612455 1.572265 4.653270 H 1.161157 3.17029 7 2.913012 H 1.128061 4.182277 1.456394 H 1.248052 3.139623 4.204571 H 1.895988 5.345392 1.246844 H 3.507408 2.214639 3.486939 H 3.150645 1.855738 5.187517 H 2.956631 0.595520 3.950109 H 2.431141 4.152444 2.839412 H 2.836917 5.758026 1.030206 H 4.823248 2.896392 1.478112 H 1.656943 4.200837 0.788616 H 2.806224 3.842286 2.083109 H 1.414006 2.785271 1.807392 H 6.842005 0.674494 0.684154 H 7.107628 2.418024 0.558489 H 7.289005 1.388456 0.874818 N 1.142036 1.580177 3.606246 O 1.906051 1.528151 4.567541 C 1.280829 0.042748 1.872719 C 1.269042 1.351818 0.988145 H 1.21 9965 0.293975 2.933105 H 2.105784 0.627206 1.645411 H 1.062578 2.167524 1.675422 C 2.609974 1.584473 0.291305 H 2.589368 2.576077 0.174850 H 2.791126 0.828954 0.475748 O 3.659004 1.510018 1. 272718 C 4.938035 1.845127 0.963850 O 5.822891 1.546045 1.732268 C 5.183804 2.613605 0.322380 H 4.646128 3.568634 0.317760 H 4.849120 2.049249 1.199051 H 6.254157 2.805307 0.402205 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2149.8297878800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2149.0050973400 a.u Ru 0.586516 0.074429 0.964139 O 0.329875 2.142198 2.244793 O 2.114022 1.809708 0.545208 O 1.101394 1.455414 2.431959 N 1.505782 2.234099 0.734849 N 0.597915 2.020943 1.298546 C 0.373552 1.529198 0.454274 C 1.408346 3.072978 1.928844 C 2.767824 1.906854 0.080253 C 3.716836 1.133499 1.032343 C 5.015529 0.750854 0.294097 C 5.715159 2.021729 0.226475 C 4.769459 2.764163 1.192213 C 3.497413 3.181296 0.423158 C 4.396348 1.836856 2.368688 C 3.682045 0.560367 1.834299 C 2.403 267 1.045041 1.130031 C 4.659006 0.169878 0.886026 C 2.030029 1.961396 1.171890 C 2.766889 1.220958 2.118159 C 4.165423 1.261885 2.058807 C 2.085717 0.422209 3.203712 C 0.794275 1.248641 0.115436 C 0.561675 2.701631 0.117077 C 0.901572 3.701422 0.809422 C 1.135801 1.234652 4.285753 C 0.106245 3.161993 2.105448 C 1.187770 2.448042 3.363792 C 0.016391 3.131333 1.358734 C 2.6890 37 2.783688 0.231959 C 4.846905 2.028291 1.107805 C 0.738869 5.060402 0.539255 C 2.611066 2.759240 2.899342

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106 C 0.135694 4.493013 1.636240 C 0.225896 5.455140 0.691109 C 4.087873 2.777495 0.20 3440 C 1.945933 3.720151 0.696899 C 6.357392 2.082327 1.076945 H 1.827235 1.665939 1.860850 H 1.181724 0.783329 0.788582 H 1.878172 4.048993 1.779743 H 1.892742 2.585006 2.785822 H 3.206735 0.234002 1.395974 H 3.950790 1.760060 1.904845 H 5.679629 0.221910 0.990267 H 5.993986 2.679607 0.609325 H 6.645334 1.751318 0.743597 H 5.263908 3.665704 1.577085 H 2.820266 3.754916 1.069935 H 3.774106 3.830381 0.420385 H 3.749105 2.367740 3.080106 H 5.302658 1.546104 2.917111 H 3.420462 0.084048 2.679750 H 4.214191 1.097832 0.522979 H 5.568420 0.434983 1.442521 H 4.735304 0.68 7349 2.785976 H 1.522771 1.073991 3.884303 H 1.374639 0.306096 2.804441 H 2.825904 0.116195 3.803948 H 1.305211 3.418803 1.774716 H 1.490073 0.340697 3.760600 H 1.778235 1.400886 5.157289 H 0.116693 1.050890 4.638470 H 0.427639 3.067812 3.146280 H 0.510661 4.101413 1.706882 H 0.771176 3.307879 3.905441 H 1.012084 5.796852 1.289082 H 2.632003 3.580984 2.179762 H 3.234645 3.032259 3.758703 H 3.048247 1.881752 2.412908 H 0.546921 4.818528 2.584048 H 0.094281 6.508211 0.924643 H 4.596140 3.391475 0.537319 H 1.867321 4.721339 0.251028 H 2.484819 3.834101 1.642839 H 0.93 5207 3.376532 0.924513 H 6.741878 1.973458 0.056534 H 6.725154 3.043945 1.457868 H 6.800541 1.293932 1.693659 N 1.921642 2.189409 1.742251 O 2.461084 3.166635 2.232078 C 1.075222 0.545531 1.982005 C 1.602430 0.824189 1.386041 H 0.945043 0.470928 3.066070 H 1.719221 1.382250 1.724405 H 1.457485 1.571798 2.163781 C 3.092727 0.768883 1.044019 H 3.412343 1.763880 0.713894 H 3.2897 36 0.048178 0.247560 O 3.807566 0.377275 2.230340 C 5.161342 0.465173 2.308195 O 5.722741 0.009238 3.267270 C 5.893762 1.186104 1.190244 H 5.604892 2.242993 1.153927 H 5.670753 0.750511 0.21 0839 H 6.963859 1.117123 1.387889 TS33 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2149.8018748300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9783633100 a.u Ru 0.324053 0.941055 0.189418 O 0.895288 4.116810 0.7 62280 O 1.041061 2.185401 1.824319 N 1.012707 0.439088 2.242464 N 1.099985 0.960637 1.967302 C 0.056079 0.234508 1.439236 C 0.815585 1.487918 3.241772 C 2.282838 0.221464 1.918464 C 3.176188 0.685181 1.034796 C 4.447743 0.076976 0.611794 C 5.231876 0.487673 1.874539 C 4.345486 1.389402 2.757950 C 3.081062 0.606064 3.184909 C 3.945692 2.645506 1.955710 C 3.147636 2.237267 0.690024 C 1.871785 1.504932 1.153052 C 4.037078 1.331932 0.186054 C 2.500112 0.691756 1.783912 C 3.314122 1.657207 1.165494 C 4.682516 1.387943 1.015399 C 2.756105 2.979311 0.693450 C 0.712604 1.6 38345 3.227744 C 3.068347 0.482267 2.331316 C 5.258732 0.201716 1.475275 C 4.434361 0.708872 2.147542 C 2.249748 1.473524 3.129047 C 6.717786 0.112172 1.243982 H 1.351935 2.155858 1.870817 H 1.204423 1.193126 4.220050 H 1.323050 2.414155 2.936974 H 2.615083 1.002350 0.147453 H 3.444468 1.597428 1.588799 H 5.068653 0.578308 0.013617 H 5.546774 0.404842 2.434968 H 6.146599 1.025762 1.591826 H 4.899441 1.682212 3.659805 H 2.453496 1.221079 3.843972 H 3.380198 0.288897 3.751924 H 3.341201 3.318835 2.578310 H 4.849652 3.201682 1.669397 H 2.869078 3.140318 0.143326

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107 H 3.5 03689 1.046571 1.100480 H 4.934725 1.882066 0.501012 H 5.310364 2.131265 0.527230 H 3.388551 3.416942 0.085885 H 2.716721 3.705875 1.517206 H 1.740488 2.881376 0.304021 H 1.040649 2.681784 3 .222680 H 1.182123 1.138150 4.084104 H 4.868365 1.625630 2.540131 H 1.911274 1.038673 4.078451 H 2.849046 2.355971 3.370797 H 1.358632 1.808865 2.591457 H 6.824823 0.894359 0.481511 H 7.197399 0.483222 2.156974 H 7.271258 0.769653 0.905270 C 0.284980 0.680629 1.617906 H 0.749482 1.496915 1.074958 C 0.965739 1.086695 2.313593 C 1.520007 2.371208 2.048926 C 1.602727 0.284177 3.277770 C 2.677863 2.787927 2.718319 C 2.750857 0.705059 3.943498 H 1.212427 0.704786 3.478219 C 3.288820 1.957813 3.659027 H 3.116163 3.756291 2.513193 H 3.219467 0.051938 4.673079 H 4.18734 5 2.301088 4.164781 O 0.853887 3.153092 1.138721 C 1.254493 4.523201 0.928348 H 1.577413 4.941440 1.889464 C 2.390842 4.602946 0.091773 H 2.706479 5.643347 0.230213 H 2.053621 4.214466 1.059 474 H 3.260387 4.019227 0.222530 C 0.011027 5.277339 0.470131 H 0.242676 6.340767 0.345593 H 0.792909 5.181796 1.206325 H 0.348174 4.890844 0.489418 C 1.147700 0.365354 2.011603 C 1.214739 1.957234 0.117613 H 1.205032 2.919248 0.637678 H 2.142346 1.717438 0.400516 H 0.822000 1.083071 2.758189 C 2.628969 0.113414 1.971221 H 2.899393 0.373378 2.919270 H 2.889453 0.558217 1.148634 O 3.361693 1.341749 1.839750 C 4.718048 1.367648 1.967794 O 5.318200 2.349735 1.601459 C 5.398658 0.165117 2.596389 H 5.237371 0.741036 2.002894 H 5.016815 0.023530 3.606084 H 6.467233 0.374 509 2.651470 N 1.180236 3.495544 1.799362 O 1.589905 4.027582 2.830483 TS34 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2149.8012715400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9751952200 a.u Ru 0.231575 0.601 904 0.648621 O 0.457559 4.118805 0.392403 O 1.116256 2.611705 0.778937 N 0.989653 2.086581 1.336027 N 1.070538 2.330460 0.633962 C 0.082829 1.401551 0.860710 C 0.854883 3.538879 1.233612 C 2.239306 1.366081 1.594195 C 3.134695 1.343226 0.330050 C 4.384772 0.478812 0.584023 C 5.179731 1.078185 1.762245 C 4.290497 1.101429 3.022736 C 3.048417 1.985297 2.756449 C 3.855864 0.340914 3.361158 C 3.046749 0.942387 2.183439 C 1.795917 0.063542 1.977583 C 3.938906 0.957032 0.925740 C 2.482817 2.107719 0.495950 C 3.095350 2.381772 0.742788 C 4.480382 2.217753 0.858325 C 2.296034 2.871828 1.926856 C 0.661495 3.682505 1.079943 C 3.261926 1.763769 1.621452 C 5.268785 1.806142 0.220010 C 4.640287 1.599794 1.451250 C 2.674559 1.636729 3.011107 C 6.752649 1.574274 0.062443 H 1.273217 0.013432 2.942778 H 1.242946 4.044701 2.121233 H 1.396246 3.920089 0.355407 H 2.561139 0.945560 0.516935 H 3.428978 2.369680 0.064474 H 5.010179 0.473160 0.319129 H 5.51 7970 2.095415 1.516122 H 6.080314 0.479106 1.952275 H 4.853249 1.528716 3.863295 H 2.418259 2.043257 3.654362 H 3.373258 3.008804 2.514077 H 3.250784 0.349473 4.278287 H 4.745605 0.954806 3. 561432 H 2.743114 1.964311 2.420671 H 3.395279 1.402478 0.084727 H 4.820529 1.588592 1.102681 H 4.952557 2.413966 1.818828 H 2.855691 2.736639 2.857823 H 2.073756 3.944579 1.838880 H 1.337563 2.356501 2.020256 H 0.954217 4.438292 0.346182 H 1.147829 3.923862 2.034534

PAGE 115

108 H 5.239486 1.303158 2.309411 H 2.716013 2.601732 3.535028 H 3.249619 0.923932 3.610582 H 1.633089 1.309173 3.00582 2 H 6.971365 0.501862 0.019353 H 7.311611 1.951776 0.925912 H 7.143123 2.063009 0.836065 C 0.422442 0.687422 1.511695 H 0.768895 0.290461 1.831518 C 0.787943 1.157600 2.237567 C 1.566324 0. 234290 2.988212 C 1.166669 2.512690 2.271381 C 2.688937 0.678081 3.701056 C 2.277683 2.950345 2.983997 H 0.575003 3.237973 1.726113 C 3.042583 2.026978 3.694895 H 3.298625 0.020026 4.260706 H 2.541607 4.003270 2.979928 H 3.917754 2.348852 4.252788 O 1.149869 1.073379 2.979474 C 1.723555 2.019528 3.908255 H 1.963700 1.487475 4.836847 C 2.984352 2.657785 3.324019 H 3.426820 3.353068 4.046620 H 2.736691 3.217236 2.415376 H 3.737209 1.908597 3.063733 C 0.642224 3.051927 4.208434 H 1.007671 3.772679 4.948144 H 0.254831 2.569605 4.608252 H 0.367282 3.601581 3.302047 C 1.376390 1.537453 0.917213 C 1.303640 1.178302 1.492962 H 1.356822 2.229606 1.798778 H 2.186933 0.586301 1.726587 H 1.139430 2.585872 0.779149 C 2.844053 1.216535 1.046899 H 3.187075 1.61 7002 2.011886 H 3.017293 0.141293 1.058386 O 3.687091 1.707451 0.003455 C 4.141394 2.995785 0.089840 O 4.875750 3.266229 1.008865 C 3.691415 4.009108 0.942783 H 3.782804 3.643450 1.970391 H 2.645540 4.282601 0.765281 H 4.309373 4.899341 0.821343 N 0.672485 3.834644 0.861038 O 1.401728 4.672698 1.384498 23 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2149.8044406900 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 2148.9824383100 a.u Ru 0.268000 0.935957 0.236282 O 0.878925 4.200811 0.968614 O 1.002318 2.189447 1.872710 N 1.008319 0.485502 2.145071 N 1.102646 1.032196 1.877716 C 0.071159 0.284486 1.356113 C 0.831712 1.552890 3.129273 C 2.249999 0.247029 1.853268 C 3.198305 0.579718 0.949939 C 4.433589 0.262997 0.573870 C 5.185065 0.662104 1.859497 C 4.245309 1.483450 2.7657 02 C 3.017414 0.620965 3.143114 C 3.794375 2.750438 2.008564 C 3.026510 2.354763 0.720054 C 1.782529 1.550371 1.147014 C 3.966550 1.526548 0.178621 C 2.501332 0.743090 1.705043 C 3.316506 1 .634734 0.987063 C 4.674411 1.323319 0.820960 C 2.782089 2.934887 0.434747 C 0.696582 1.725271 3.122588 C 3.066305 0.388053 2.341171 C 5.241123 0.170022 1.365909 C 4.421210 0.658557 2.141160 C 2.268130 1.284156 3.264677 C 6.685032 0.197992 1.120123 H 1.258466 2.140329 1.907939 H 1.221884 1.267793 4.109880 H 1.349508 2.467401 2.807669 H 2.670736 0.894536 0.042843 H 3.506203 1.4959 05 1.476548 H 5.091487 0.334602 0.071030 H 5.537915 0.234925 2.389245 H 6.074564 1.255439 1.608387 H 4.773054 1.765764 3.686514 H 2.353422 1.175874 3.819746 H 3.355870 0.280534 3.676799 H 3 .154373 3.370635 2.650672 H 4.673911 3.358530 1.753538 H 2.710434 3.263269 0.202442 H 3.454711 1.249527 1.106634 H 4.838172 2.131881 0.464468 H 5.300971 2.007584 0.251182 H 3.244021 3.179710 0.528174 H 3.013078 3.766109 1.115887 H 1.699580 2.908297 0.302419 H 1.008784 2.773676 3.100146 H 1.165972 1.248825 3.992257 H 4.848730 1.548058 2.598548 H 2.216653 0.855877 4.275214 H 2.7471 47 2.263546 3.356436 H 1.243052 1.444072 2.922828 H 6.748824 1.074277 0.462349 H 7.197476 0.458068 2.053642 H 7.236316 0.622064 0.648713 C 0.314909 0.857280 1.754317

PAGE 116

109 H 0.875263 1.611793 1.215858 C 1.033792 1.289707 2.180635 C 1.485128 2.602063 1.858388 C 1.882600 0.471569 2.951433 C 2.749804 3.029852 2.280438 C 3.135921 0.906830 3.375044 H 1.568593 0.537978 3.189245 C 3.56809 4 2.185829 3.033687 H 3.113686 4.017422 2.026618 H 3.766456 0.244434 3.959765 H 4.545636 2.540608 3.349212 O 0.619547 3.393556 1.150785 C 0.919821 4.791263 0.942678 H 1.451478 5.165348 1.825 445 C 1.780183 4.970807 0.308478 H 2.029161 6.028299 0.452952 H 1.233251 4.624140 1.192875 H 2.713769 4.404508 0.242020 C 0.415448 5.520947 0.844008 H 0.244871 6.599085 0.750824 H 1.019758 5.342232 1.738543 H 0.982141 5.187687 0.030900 C 1.011416 0.239124 2.224726 C 1.085272 2.096472 0.145523 H 1.016798 3.089498 0.309255 H 1.967557 1.911739 0.758567 H 0.564621 0.935536 2.926480 C 2.511631 0.239301 2.163275 H 2.881301 0.013129 3.167132 H 2.870483 0.517014 1.458327 O 3.029075 1.525422 1.780738 C 4.367894 1.777914 1.815763 O 4.792827 2.750026 1.238383 C 5.251891 0.832 792 2.609896 H 5.221387 0.182529 2.200281 H 4.935200 0.780393 3.657631 H 6.274169 1.209017 2.563384 N 1.196653 3.489035 1.935123 O 1.688983 3.923927 2.976736 24 B3LYP/SDD/6 31G(d) SCF energy in gas p has e: 2149.8080097200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2148.9823569000 a.u Ru 0.118944 0.902506 0.265626 O 0.065925 3.903035 2.222813 O 0.797238 2.898893 0.420391 N 1.124688 1.270925 1.840659 N 0. 920862 1.909940 1.358029 C 0.006154 0.896647 1.195973 C 1.114469 2.661900 2.290945 C 2.265459 0.344368 1.883030 C 3.253412 0.605105 0.720492 C 4.369844 0.458765 0.730961 C 5.130250 0.383736 2.070006 C 4.147921 0.642376 3.230933 C 3.044813 0.443216 3.215224 C 3.523321 2.044965 3.062467 C 2.748216 2.121173 1.721164 C 1.627851 1.064929 1.778184 C 3.734533 1.854669 0.565992 C 2.3527 08 1.780942 1.282684 C 3.055402 2.402206 0.234271 C 4.449435 2.271487 0.186597 C 2.360329 3.248493 0.805086 C 0.383635 2.996083 2.209594 C 3.053046 1.128377 2.323482 C 5.160952 1.567940 1.15 9252 C 4.442859 1.022801 2.229075 C 2.364164 0.599173 3.564312 C 6.656921 1.387284 1.059871 H 1.081432 1.221179 2.715544 H 1.517703 2.762365 3.302178 H 1.713211 3.292630 1.619087 H 2.718194 0.576328 0.234935 H 3.684544 1.612943 0.818667 H 5.059667 0.261411 0.100156 H 5.604254 0.601919 2.185480 H 5.935566 1.130296 2.089010 H 4.683331 0.586002 4.188023 H 2.355067 0.301913 4.058301 H 3.508781 1.434684 3.330713 H 2.848611 2.263504 3.901570 H 4.317727 2.804609 3.086242 H 2.306409 3.114690 1.601526 H 3.216463 1.929079 0.395335 H 4.521315 2.622249 0.565812 H 4.989589 2.73 6463 0.636004 H 2.793283 3.093977 1.799737 H 2.478846 4.316108 0.571839 H 1.291962 3.037827 0.859146 H 0.581371 3.972553 1.757745 H 0.863303 2.974619 3.196310 H 4.980430 0.497003 3.015443 H 2.316159 1.375365 4.340795 H 2.924121 0.240398 3.987932 H 1.343754 0.259594 3.374673 H 6.903683 0.387639 0.679682 H 7.139884 1.488702 2.038185 H 7.105812 2.119542 0.380909 C 0.342486 0.162831 1.845979 H 0.805784 1.122372 1.654927 C 1.025248 0.224838 2.408483 C 1.650950 1.484198 2.635205 C 1.731508 0.937689 2.779552 C 2.945291 1.537421 3.167976 C 3.012381 0.875349 3.322812 H 1.278372 1.911315 2.628643 C 3.620255 0.363810 3.508003

PAGE 117

110 H 3.442388 2.487223 3.318317 H 3.526853 1.792295 3.592795 H 4.623269 0.430805 3.920999 O 0.921091 2.601101 2.324056 C 1.401430 3.907902 2.711985 H 1.952488 3.806772 3.654028 C 2.312448 4.481908 1.626467 H 2.705449 5.458054 1.932835 H 1.748497 4.617056 0.696362 H 3.158829 3.820318 1.419401 C 0.175565 4.777732 2.969026 H 0.488 457 5.760210 3.339345 H 0.473785 4.315944 3.718907 H 0.402722 4.926589 2.052178 C 1.142582 0.965203 1.833367 C 1.310798 1.634248 1.125602 H 1.392484 2.728266 1.091589 H 2.116112 1.116309 1.6 46353 H 0.778470 1.892541 2.263628 C 2.640080 0.827858 1.718248 H 3.075892 0.920616 2.722162 H 2.899551 0.158979 1.330481 O 3.295907 1.741115 0.828166 C 3.743317 2.990306 1.181404 O 4.405114 3.588646 0.369560 C 3.362864 3.553781 2.533756 H 3.554276 2.859573 3.358211 H 2.298603 3.818638 2.544900 H 3.948300 4.460977 2.687358 N 0.011159 3.778029 0.979576 O 0.748450 4.448389 0.274646 TS14 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3065853700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.5331761400 a.u Ru 0.679839 0.349779 0.028032 O 2.438615 3.597161 0.537254 O 1.452031 2.286100 0.924846 N 1.478318 2.335280 0.327653 N 0.708844 2.569411 0.243715 C 0.312613 1.639670 0.231114 C 1.300242 3.754649 0.633626 C 2.714506 1.677559 0.130379 C 3.503509 1.026819 1.033713 C 4.732077 0.2 71209 0.483236 C 5.642964 1.259298 0.272555 C 4.855029 1.889300 1.439038 C 3.649261 2.665679 0.865619 C 4.364238 0.784007 2.398667 C 3.446550 0.209491 1.637696 C 2.226854 0.584654 1.126127 C 4.260202 0.832507 0.483085 C 2.035241 2.452766 0.307992 C 3.146177 2.787290 0.492222 C 4.426965 2.706762 0.066348 C 2.999546 3.295127 1.907493 C 0.177565 3.954951 0.285466 C 2.208888 2.189318 1.687268 C 4.635793 2.346304 1.398284 C 3.509098 2.120508 2.195306 C 1.045942 2.028000 2.639898 C 6.028645 2.213578 1.965937 H 1.760385 1.101988 1.976472 H 1.960336 4.386765 0.037155 H 1.5 03725 3.951238 1.694829 H 2.847221 0.336443 1.583874 H 3.810706 1.803901 1.748901 H 5.283342 0.175712 1.320707 H 6.008489 2.045175 0.404067 H 6.525923 0.732173 0.657191 H 5.498738 2.593277 1 .982750 H 3.098461 3.164716 1.674549 H 4.013304 3.445184 0.179949 H 3.824907 1.232264 3.245151 H 5.227754 0.248964 2.817786 H 3.111163 1.001004 2.314668 H 3.668403 1.587244 0.040800 H 5.134965 1.354438 0.895618 H 5.283678 2.941588 0.561833 H 3.870777 3.024189 2.511516 H 2.934511 4.392228 1.918670 H 2.106712 2.903771 2.395986 H 0.710263 4.551245 1.029360 H 0.314572 4.429734 0.695509 H 3.643125 1.902154 3.252802 H 0.247503 2.750122 2.437688 H 1.380521 2.180021 3.670680 H 0.592184 1.034075 2.575489 H 6.367503 1.169982 1.930195 H 6.066860 2.530563 3.013890 H 6.7515 27 2.812071 1.401902 C 0.991634 0.802456 0.742215 H 1.866843 0.188631 0.516317 N 1.648499 3.471062 0.414476 O 1.038022 4.428230 0.915136 C 0.823123 0.497761 3.816995 C 0.270500 1.499120 3.36 1203 C 1.600164 2.350525 2.406763 C 2.124140 1.075739 3.126253 H 0.930682 0.658100 4.898254 H 2.782341 1.447811 3.922541 C 0.542471 2.830855 3.456878 H 0.024953 3.709265 3.135636 H 0.972038 3.020175 4.449668 C 0.559866 1.566004 1.845170 C 0.606007 2.126940 1.264532 H 1.183186 1.441204 3.961686 H 2.396269 3.051102 2.143957

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111 C 2.964999 0.137372 2.270283 H 2.382016 0.348313 1.488632 H 3.421549 0.644952 2.885713 H 3.776411 0.690944 1.783172 C 0.492971 0.981044 3.636454 H 0.449909 1.217770 4.146537 H 1.270610 1.613505 4.080505 H 0.383435 1.252335 2.586791 C 1.304738 1.88 0892 1.745603 H 1.335245 1.416109 2.745234 O 2.618826 2.390424 1.429980 C 3.053109 3.595049 1.907105 O 4.163042 3.960608 1.601346 C 2.110748 4.396110 2.782585 H 1.789578 3.818574 3.656924 H 1.206535 4.685444 2.234938 H 2.638993 5.290605 3.113820 H 0.551687 2.665666 1.756931 H 1.536929 1.978750 1.583547 H 0.574661 2.870871 0.481535 TS15 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3587097700 00 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.57641953000 a.u Ru 0.583365 0.330095 0.244976 O 1.023645 0.139792 2.473509 O 1.303691 1.862642 1.687766 N 1.478045 1.989810 1.255922 N 0.709496 2.1647 90 1.340221 C 0.321012 1.399832 0.831954 C 1.281515 3.265724 1.946205 C 2.744423 1.662931 0.593269 C 2.966145 2.598742 0.627758 C 4.258014 2.207105 1.371162 C 5.458890 2.303225 0.411009 C 5.232710 1.352118 0.782533 C 3.958827 1.791228 1.542015 C 5.075182 0.092493 0.257503 C 3.849968 0.182189 0.695262 C 2.609088 0.208590 0.140016 C 4.109033 0.764543 1.887952 C 2.033571 2.380637 0.831934 C 2.215053 2.901282 0.468056 C 3.509868 3.246038 0.871340 C 1.061588 3.118346 1.418218 C 0.206757 3.202686 2.275746 C 3.126836 2.257308 1.712615 C 4.618370 3.103935 0.030952 C 4.401 342 2.612226 1.258707 C 2.955926 1.767294 3.132636 C 6.007792 3.458668 0.507064 H 2.665059 0.400345 1.056678 H 1.907823 3.334726 2.839338 H 1.528834 4.109519 1.287264 H 2.106666 2.515190 1.3 02513 H 3.032726 3.644538 0.296001 H 4.404869 2.891695 2.217051 H 5.583804 3.335827 0.054253 H 6.383956 2.033233 0.937969 H 6.090078 1.404908 1.466600 H 3.798207 1.161901 2.427914 H 4.083179 2.826413 1.893482 H 4.953032 0.788731 1.099014 H 5.989441 0.392918 0.273826 H 3.748875 1.212429 1.054315 H 3.295364 0.716067 2.614906 H 5.027199 0.455763 2.406873 H 3.651229 3.650585 1.871471 H 0.633663 2.170830 1.762572 H 1.391666 3.679749 2.297561 H 0.248234 3.683129 0.947218 H 0.727945 4.148435 2.111342 H 0.377496 2.887507 3.311871 H 5.245273 2.504927 1.937537 H 2.740768 2.5 95346 3.821487 H 3.871607 1.284575 3.488250 H 2.134564 1.049753 3.219281 H 6.515186 2.584842 0.937217 H 6.633017 3.823972 0.314769 H 5.980124 4.231565 1.282452 C 0.151414 1.491145 1.184503 H 0.533605 1.280267 2.014116 N 1.390561 1.067086 2.704306 O 1.796188 1.443017 3.787819 C 3.551337 2.814844 0.601564 C 2.505573 2.262870 0.435197 C 2.923423 0.446419 0.848519 C 3.866663 1.541010 1.480404 H 4.449333 3.056282 0.017681 H 4.892033 1.220110 1.251869 C 3.028784 0.835075 0.639899 H 2.389410 0.238538 1.288580 H 4.055501 0.801758 1.019621 C 1.227310 1.993987 0.358396 C 1.4 97935 0.863931 1.186159 H 2.384092 2.896353 1.315001 H 3.208714 0.567774 1.122964 H 0.631390 2.820196 0.728299 C 3.776112 1.694857 3.001375 H 4.521203 2.409455 3.369836 H 3.972943 0.733856 3 .492724 H 2.794850 2.042580 3.338196 C 3.136940 4.094298 1.335426 H 2.891547 4.883425 0.614510 H 3.952449 4.466890 1.965758 H 2.265338 3.950335 1.982000 C 0.922901 2.760828 1.410153 H 1.729359 2.518059 2.123500

PAGE 119

112 O 0.062994 3.765886 1.989579 C 0.477264 5.051327 2.176342 O 0.296997 5.840754 2.661042 C 1.888513 5.412618 1.752747 H 2.633677 4.762875 2.224575 H 2.010145 5.316643 0.6675 31 H 2.073767 6.447441 2.041286 H 1.158716 0.822263 2.214766 H 1.385555 3.126771 0.489472 TS16 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3283009800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.5439607700 a.u Ru 0.505746 0.281554 0.225159 O 1.516597 0.359691 2.283272 O 1.201155 2.163739 1.124694 N 1.619437 2.238320 0.699780 N 0.510847 2.684373 0.511154 C 0.421749 1.683075 0.369909 C 1.572058 3.691488 0.883519 C 2.875746 1.510856 0.496381 C 3.554326 1.933603 0.833225 C 4.851620 1.124981 1.043480 C 5.814717 1.361554 0.135522 C 5.133558 0.913040 1.444093 C 3.866563 1.770924 1.659583 C 4.761856 0.583688 1.342990 C 3.771850 0.807669 0.165057 C 2.503384 0.019070 0.491683 C 4.494467 0.369959 1.130695 C 1.939829 2.660542 0.392193 C 2.523235 3.091268 0.819426 C 3.916073 3.132 085 0.912935 C 1.676624 3.554461 1.984270 C 0.073044 3.929815 1.052043 C 2.742706 2.362894 1.510011 C 4.742971 2.786500 0.164039 C 4.135843 2.418327 1.365521 C 2.162869 2.027828 2.866981 C 6.247094 2.806808 0.023270 H 2.257635 0.231853 1.534782 H 2.151987 4.005705 1.754894 H 1.974397 4.205379 0.000006 H 2.864842 1.760726 1.666627 H 3.789059 3.007667 0.807274 H 5.326009 1.448186 1.979418 H 6.093476 2.423434 0.199203 H 6.743448 0.796211 0.020320 H 5.816594 1.067342 2.290142 H 3.381161 1.519198 2.612362 H 4.154324 2.831784 1.708625 H 4.314007 0.925422 2.286659 H 5.673 196 1.178900 1.188848 H 3.517368 1.871681 0.104679 H 3.888501 0.550905 2.018735 H 5.411011 0.965285 1.247169 H 4.368889 3.453274 1.848711 H 0.836591 2.884437 2.188516 H 2.279876 3.632930 2.8 93645 H 1.249365 4.547910 1.791015 H 0.292978 4.799659 0.499588 H 0.213316 4.050294 2.105659 H 4.758939 2.173257 2.223491 H 2.324467 2.856356 3.569070 H 2.651302 1.146762 3.298087 H 1.089955 1.830969 2.824590 H 6.612685 1.879844 0.437680 H 6.739313 2.903652 0.996257 H 6.579433 3.636116 0.610727 C 0.415298 0.895257 1.318252 H 0.974750 0.274427 2.024052 N 1.708094 1.621376 2.183035 O 2.323324 2.268680 3.011245 C 2.586270 2.978634 1.383762 C 3.021632 1.676794 0.640034 C 2.202765 0.898724 2.606534 C 2.101710 2.440889 2.787651 H 3.526673 3.524766 1.539938 H 2.905264 2.6 56594 3.505292 C 3.584109 0.867648 1.859006 H 3.915863 0.140532 1.593916 H 4.393049 1.383085 2.394440 C 1.955507 0.625748 0.263803 C 1.397295 0.173727 1.494375 H 3.714132 1.875245 0.182232 H 2.154953 0.364015 3.560020 C 0.846396 3.058026 3.402165 H 0.022026 3.150855 2.701572 H 1.069929 4.065600 3.774355 H 0.505360 2.465802 4.259352 C 1.654219 3.949491 0.660452 H 2.036968 4.168223 0.342538 H 1.600326 4.897773 1.208429 H 0.636624 3.567178 0.581693 C 0.207703 2.256442 1.909076 H 0.594842 2.132804 2.656707 O 1.417078 2.684309 2.575178 C 1.467571 3.834926 3.304582 O 2.5 03948 4.126112 3.851988 C 0.213034 4.684455 3.378471 H 0.623354 4.129143 3.817589 H 0.101334 5.015352 2.382427 H 0.429509 5.556030 3.996541 H 0.120672 2.998855 1.181477 H 1.277429 0.886297 1 .675805 H 2.292370 0.099028 0.464038 TS14E

PAGE 120

113 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.2977634100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.5159604900 a.u Ru 0.700700 0.037581 0.728479 O 1.424767 1.096646 2.563233 O 0.926454 1.006206 2.730622 N 1.963196 1.361884 1.427915 N 0.080512 2.175565 1.331466 C 0.755687 1.232727 0.782849 C 2.052862 2.583157 2.230011 C 3.126419 0.712245 0.807738 C 3.824871 1.658604 0.205796 C 4.973507 0.916614 0.917709 C 5.999055 0.433456 0.126377 C 5.302677 0.515244 1.123647 C 4.172544 0.252869 1.849912 C 4.726103 1.722021 0.349289 C 3.679299 1.233801 0.690347 C 2.551750 0.539205 0.102726 C 4.391813 0.289617 1.680520 C 1.415651 2.503279 0.935275 C 1.630801 3.206001 0.272675 C 2.934249 3.596803 0.593642 C 0.489107 3.596198 1.181359 C 0.57 2770 2.952643 2.404648 C 2.487708 2.250388 1.815258 C 4.020269 3.341472 0.251208 C 3.772359 2.673602 1.451450 C 2.290117 1.585544 3.159558 C 5.417651 3.771160 0.131044 H 2.274908 1.234174 0. 910591 H 2.556932 2.405152 3.184521 H 2.604643 3.367719 1.692952 H 3.095425 2.015396 0.940796 H 4.225225 2.537115 0.320463 H 5.459782 1.601748 1.624549 H 6.434035 1.291102 0.659303 H 6.827967 0.087858 0.371661 H 6.028917 0.868140 1.868067 H 3.687523 0.388213 2.598132 H 4.600176 1.113752 2.385720 H 4.263295 2.434168 1.046577 H 5.541653 2.258045 0.156826 H 3.273223 2.097751 1.231434 H 3.707136 0.062824 2.455820 H 5.198748 0.833958 2.190838 H 3.099587 4.143267 1.520080 H 0.831025 4.306773 1.940211 H 0.323892 4.069305 0.617643 H 0.049780 2.736438 1.697122 H 0.3796 16 4.022088 2.276762 H 0.193826 2.653607 3.389852 H 4.598273 2.477939 2.132646 H 2.138542 2.330484 3.952685 H 3.172089 0.999326 3.437134 H 1.423463 0.920738 3.166353 H 6.065210 3.856948 0.74 7778 H 5.412655 4.739137 0.644319 H 5.883641 3.046756 0.812110 N 1.328949 0.064098 3.328948 O 1.593390 0.093743 4.515630 C 4.489509 1.484513 1.361286 C 3.432573 1.926810 2.436032 C 2.784087 3.109678 0.608428 C 4.057997 2.336134 0.106371 H 5.459004 1.850284 1.722630 H 4.808155 3.127051 0.021195 C 3.263314 3.433625 2.050432 H 2.512837 3.948532 2.659061 H 4.206600 3.991299 2.095847 C 2.077213 1.433767 2.052117 C 1.570469 2.203903 0.978855 H 3.727430 1.680066 3.459064 H 2.524599 3.957265 0.026065 C 4.025010 1.576921 1.219663 H 3.426061 0.664472 1.168416 H 5.042506 1.27 4182 1.496834 H 3.628497 2.208984 2.017087 C 4.598775 0.031909 1.198561 H 4.876779 0.493938 2.154145 H 5.370255 0.297337 0.468100 H 3.661459 0.491318 0.870145 H 1.497823 0.718897 2.626218 H 0.740011 2.801557 1.372630 C 0.196641 1.564636 0.181630 H 0.438679 2.459005 0.104121 C 0.716022 1.515328 1.595597 H 1.504217 0.780460 1.728143 H 0.127484 1.226184 2.233497 O 1.285937 2.764093 2.071332 C 0.548717 3.769310 2.609208 O 1.066025 4.854983 2.743084 C 0.870651 3.470910 3.058689 H 0.886981 2.676220 3.813519 H 1.504055 3.147243 2.226158 H 1.282376 4.383831 3.489921 TS15E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3530540100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.5724041600 a.u Ru 0.621100 0.523174 0.601819 O 1.291843 0.612974 2.508338 O 1.158787 1.553453 2.487633 N 1.790664 0.870494 1.661804 N 0.282591 1.605062 1.644894 C 0.598126 0.761386 0.998476 C 1.759124 1.752171 2.830752 C 3.036286 0.595664 0.932710 C 3.506569 1.888497 0.211146

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114 C 4.761725 1.604940 0.634660 C 5.885804 1.073064 0.275337 C 5.413050 0.221733 0.967038 C 4.178404 0.095342 1.846857 C 5.055901 1.265839 0.115695 C 3.903828 0.730148 1.011607 C 2.694855 0.501932 0.076481 C 4.397 439 0.557899 1.704110 C 1.488607 2.220561 1.159260 C 1.433663 3.111087 0.063047 C 2.592893 3.812197 0.282374 C 0.165594 3.344229 0.722025 C 0.366562 2.379250 2.731950 C 2.668169 2.093507 1.9 16668 C 3.792085 3.671331 0.425195 C 3.804330 2.811019 1.524269 C 2.739848 1.224433 3.152091 C 5.033697 4.422382 0.004258 H 2.604327 1.428062 0.507978 H 1.891918 1.171827 3.752004 H 2.557169 2.499118 2.789462 H 2.698170 2.251044 0.433147 H 3.724513 2.674819 0.948576 H 5.086642 2.535456 1.118919 H 6.157529 1.828208 1.027270 H 6.788291 0.873976 0.317935 H 6.213888 0.613066 1.608336 H 3.849446 0.801124 2.389722 H 4.449786 0.852314 2.598244 H 4.761087 2.214975 0.352631 H 5.944130 1.475719 0.728329 H 3.656493 1.487880 1.762709 H 3.630571 0.959912 2.371343 H 5.277793 0.3 27863 2.320251 H 2.552222 4.497795 1.126320 H 0.682129 3.573873 0.065776 H 0.116177 2.467010 1.312912 H 0.291280 4.186960 1.408525 H 0.398109 3.440756 2.456377 H 0.204746 2.290862 3.660215 H 4.719120 2.698305 2.103016 H 2.626251 1.823022 4.066139 H 3.709929 0.720762 3.219369 H 1.954657 0.463845 3.158161 H 5.548580 3.908246 0.818130 H 5.746770 4.513628 0.830029 H 4.791118 5.430871 0.348650 N 1.458680 0.485709 3.151755 O 1.871774 0.526658 4.295183 C 0.020181 2.067529 0.314084 H 0.337857 3.023186 0.127052 C 0.509017 2.282363 1.698062 H 1.207693 1.502007 2.007303 H 0.3 65308 2.240491 2.366636 O 1.136574 3.579453 1.794975 C 1.523672 4.107859 2.990287 O 2.092209 5.172260 2.996792 C 1.205340 3.324274 4.251114 H 1.642739 2.320071 4.224186 H 0.123358 3.209146 4 .383607 H 1.612066 3.872751 5.100965 C 3.824014 1.974192 1.735522 C 2.781904 1.943004 0.557818 C 2.762597 0.201350 1.285464 C 3.825136 0.474278 2.233139 H 4.795261 2.175848 1.264683 H 4.793336 0.031689 1.962211 C 3.059758 0.549908 0.025405 H 2.381128 0.275278 0.829867 H 4.092295 0.425235 0.369368 C 1.415222 1.729134 1.208204 C 1.407218 0.372042 1.680334 H 2.856954 2.801129 0.111424 H 2.838868 1.287527 1.266346 H 0.978495 2.510592 1.819321 H 1.016991 0.140373 2.664807 C 3.629157 0.231196 3.732793 H 4.461019 0.650565 4.310441 H 3.595286 0.845189 3.942241 H 2.70653 2 0.672373 4.121538 C 3.603024 3.067337 2.786115 H 3.579337 4.054603 2.308935 H 4.418999 3.075838 3.517575 H 2.668380 2.944944 3.342258 TS16E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3312533000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.5480882800 a.u Ru 0.564699 0.619220 0.055936 O 1.409819 1.487849 1.867161 O 1.306928 2.700430 0.072941 N 1.594428 2.088611 0.105294 N 0.544255 2.312193 0.5 57014 C 0.433568 1.389721 0.240191 C 1.497676 3.499772 0.484814 C 2.876522 1.372562 0.065634 C 3.466220 1.235450 1.494767 C 4.779171 0.427415 1.449171 C 5.793355 1.134023 0.529118 C 5.201360 1.241863 0.890659 C 3.911859 2.092730 0.830657 C 4.887710 0.175724 1.420959 C 3.847162 0.871750 0.498873 C 2.566136 0.005091 0.542064 C 4.475663 0.982645 0.908186 C 1.818219 2.094847 1.187179 C 1.848398 1.768860 2.562929 C 3.088062 1.636042 3.192205

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115 C 0.577163 1.583079 3.361338 C 0.017458 3.696043 0.609511 C 3.010737 2.351565 0.486877 C 4.293427 1.842698 2.510024 C 4.229260 2.2 12807 1.165915 C 3.034036 2.762068 0.969298 C 5.619484 1.674410 3.214264 H 2.382800 0.178429 1.609216 H 1.942661 4.145591 0.277805 H 2.020679 3.686230 1.431844 H 2.738602 0.730581 2.139004 H 3.660659 2.230522 1.920749 H 5.189439 0.354813 2.465055 H 6.033222 2.134694 0.917129 H 6.734298 0.568013 0.502793 H 5.922136 1.734627 1.556836 H 3.490528 2.230349 1.836087 H 4.153867 3.091860 0.437720 H 4.504289 0.118874 2.449326 H 5.814102 0.766380 1.459761 H 3.629926 1.872171 0.888768 H 3.822272 1.509136 1.605723 H 5.405850 1.564486 0.843537 H 3.112546 1.378125 4.248955 H 0.069303 2.467694 3.305334 H 0.017043 0.732665 3.008832 H 0.810322 1.411662 4.416250 H 0.311361 4.179765 1.545661 H 0.427673 4.290352 0.216542 H 5.152132 2.409066 0.623879 H 3.904862 3.392916 1.174343 H 3.108462 1.891616 1.633976 H 2.139123 3.318554 1.259847 H 5.880295 0.613096 3.317661 H 6.430830 2.159519 2.662459 H 5.593377 2.099388 4.223977 N 1.651247 2.622546 1.312503 O 2.16 8215 3.550282 1.906422 C 0.199180 0.582142 1.781492 H 0.238877 1.532934 2.324159 C 0.584658 0.548078 2.682159 H 0.804761 1.467064 2.134146 H 0.291839 0.732054 3.323647 O 1.729207 0.181140 3. 486429 C 2.073654 0.862063 4.616856 O 3.089146 0.552317 5.190698 C 1.145467 1.962571 5.097782 H 0.960047 2.710983 4.319821 H 0.174365 1.552971 5.399393 H 1.609934 2.441596 5.959980 C 2.422028 3.469333 0.910606 C 2.921293 1.987008 0.816099 C 2.377471 2.491531 1.324479 C 2.158987 3.852054 0.599041 H 3.303712 4.029435 1.250237 H 3.017906 4.453239 0.927674 C 3.673807 2.052159 0.55498 1 H 4.066288 1.082444 0.876615 H 4.482020 2.795069 0.582937 C 1.909313 0.914453 0.374876 C 1.516451 1.263584 0.932101 H 3.501298 1.679943 1.689708 H 2.467627 2.601892 2.409181 H 2.143903 0. 107522 0.637111 H 1.375647 0.516038 1.700084 C 0.933326 4.699258 0.936364 H 1.057511 5.712524 0.533896 H 0.829182 4.796673 2.023954 H 0.003798 4.299712 0.540081 C 1.305509 3.801581 1.903426 H 1.539300 3.401119 2.897528 H 1.209167 4.888988 2.004505 H 0.330841 3.424690 1.590172 TS8 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3741261500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.5914714300 a.u Ru 0.627564 0.374758 0.282323 O 1.288922 0.077995 2.440587 O 1.281533 1.959140 1.700132 N 1.738040 1.754578 1.330742 N 0.421617 2.119801 1.396330 C 0.544023 1.308976 0.852639 C 1.647273 3.007609 2.084080 C 2.984123 1.288743 0.711432 C 3.373777 2.224220 0.463183 C 4.648456 1.704958 1.157371 C 5.801524 1.631773 0.137144 C 5.406817 0.679948 1.009636 C 4.155248 1.245121 1.721591 C 5.1 10766 0.721181 0.429414 C 3.930789 0.640846 0.579431 C 2.699965 0.137684 0.213415 C 4.360293 0.302989 1.725603 C 1.784988 2.312583 0.999739 C 2.056557 3.027292 0.187526 C 3.387561 3.315321 0 .502308 C 0.942893 3.525745 1.080842 C 0.142016 3.102659 2.349947 C 2.825526 1.946802 1.874034 C 4.447252 2.939188 0.332436 C 4.142594 2.262984 1.515894 C 2.558201 1.258479 3.193192 C 5.877531 3.240932 0.048725 H 2.655110 0.771672 1.112158 H 2.233421 2.960380 3.005676 H 2.018026 3.851856 1.486796 H 2.545187 2.263018 1.179936

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116 H 3.542493 3.244633 0.089700 H 4.918338 2.389109 1.9727 98 H 6.027334 2.631800 0.260713 H 6.714651 1.269647 0.628464 H 6.228446 0.613496 1.735289 H 3.876903 0.615669 2.577865 H 4.382522 2.248330 2.112997 H 4.870582 1.423230 1.240063 H 6.009953 1 .107331 0.071622 H 3.732607 1.641782 0.977626 H 3.590327 0.369677 2.496641 H 5.264413 0.098280 2.204635 H 3.601405 3.865599 1.416147 H 0.317942 2.712951 1.465318 H 1.351313 4.071229 1.936645 H 0.274939 4.208736 0.540370 H 0.267807 4.098392 2.158755 H 0.113370 2.818745 3.378390 H 4.949185 1.973471 2.186425 H 2.439535 1.988964 4.005018 H 3.392002 0.605321 3.469172 H 1.647049 0.655326 3.162795 H 6.284745 2.456422 0.700071 H 6.523929 3.301361 0.832868 H 5.955661 4.187565 0.594232 C 0.059285 1.376098 1.167626 H 0.525338 0.970522 2.074413 N 1.517416 1.161144 2.685530 O 1.933676 1.557393 3.759397 C 3.322184 1.153817 2.627028 C 1.755189 1.229354 2.486050 C 2.459564 2.220209 0.577500 C 3.814404 1.838045 1.286920 H 3.583017 1.820285 3.459506 H 4.283985 2.79 4658 1.550264 C 1.627110 2.612624 1.811934 H 0.599473 2.895179 1.600304 H 2.102777 3.408033 2.396463 C 1.378320 0.271613 1.354464 C 1.814359 0.898947 0.160665 H 1.226021 1.080538 3.430217 H 2.578764 2.959850 0.215858 H 1.471247 0.797431 1.496881 C 4.823491 1.070312 0.429518 H 5.764125 0.921788 0.972966 H 5.058332 1.638764 0.479167 H 4.462328 0.085194 0.121036 C 3.896565 0.224629 2.964662 H 3.444325 0.606827 3.888490 H 4.978966 0.168457 3.130918 H 3.721385 0.964048 2.177743 C 0.166454 2.852996 1.311706 H 1.134114 2.972625 1.826418 O 0.884277 3.429212 2.119810 C 0.851073 4.731259 2.524324 O 1.769994 5.153506 3.183864 C 0.347212 5.569977 2.121858 H 1.274921 5.164749 2.541921 H 0.468960 5.602957 1.033667 H 0.195414 6.581004 2.500287 H 2.212319 0.325847 0.665598 H 0.234429 3.363355 0.347110 8 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3886528700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6110002300 a.u Ru 0.689233 0.386583 0.243773 O 1.661470 0.395867 2.500652 O 1.416866 2.180248 1.283343 N 1.694238 1.956044 1.112647 N 0.461299 2.307245 1.084947 C 0.511182 1.434099 0.680831 C 1.586613 3.294502 1.699161 C 2.967338 1.394372 0.666656 C 3.54248 4 2.198758 0.530912 C 4.860261 1.559874 1.013923 C 5.882658 1.535404 0.139210 C 5.310154 0.713227 1.311964 C 4.014130 1.385615 1.811417 C 5.004706 0.722376 0.836958 C 3.963607 0.689165 0.317991 C 2.683975 0.049121 0.244467 C 4.569146 0.124208 1.485372 C 1.864513 2.369061 0.792151 C 2.271609 3.023092 0.391941 C 3.636662 3.222902 0.607748 C 1.260541 3.544644 1.388111 C 0.07380 8 3.432171 1.884478 C 2.807288 1.971628 1.757699 C 4.602329 2.815843 0.322550 C 4.165568 2.199892 1.496027 C 2.413104 1.331645 3.070144 C 6.073898 3.019043 0.049472 H 2.380944 0.630036 1.150 802 H 2.134174 3.360976 2.643306 H 1.991629 4.052842 1.016230 H 2.806501 2.209744 1.343809 H 3.721653 3.239593 0.227229 H 5.257948 2.151720 1.848592 H 6.112861 2.557872 0.471768 H 6.826143 1.092267 0.206153 H 6.036277 0.684188 2.134963 H 3.602422 0.846374 2.675307 H 4.235414 2.411083 2.140906 H 4.626554 1.326067 1.673623 H 5.926892 1.205573 0.486153 H 3.758653 1.714122 0.639143 H 3.887288 0.138693 2.338317

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117 H 5.499185 0.358420 1.815225 H 3.955412 3.724289 1.519015 H 0.571759 2.764530 1.727727 H 1.763964 3.958279 2.266707 H 0.646310 4.344162 0.953288 H 0.321088 4.383 226 1.515775 H 0.231295 3.323824 2.933026 H 4.897918 1.888226 2.238268 H 2.743336 1.945662 3.917264 H 2.885227 0.348759 3.183999 H 1.333893 1.190372 3.152433 H 6.482789 2.181714 0.531178 H 6.649454 3.083594 0.978590 H 6.252661 3.932695 0.527593 C 0.556018 1.264390 1.067097 H 0.840216 0.719245 1.968473 N 1.821686 1.652173 2.398681 O 2.328858 2.339041 3.270794 C 2.935561 1.091460 2.813526 C 1.403741 1.263498 2.516304 C 2.367549 2.218948 0.703129 C 3.602840 1.741585 1.531524 H 3.143755 1.750394 3.667073 H 4.109473 2.660959 1.853579 C 1.435079 2.655508 1.846921 H 0.459963 3.019020 1.535700 H 1.900915 3.412701 2.489078 C 1.027190 0.308424 1.376188 C 1.639581 0.987529 0.084101 H 0.787134 1.155547 3.412778 H 2.625695 2.975446 0.041816 H 1.356721 0.714687 1.538742 C 4.650988 0.914304 0.782624 H 5.528179 0.733339 1.415787 H 4.995598 1.456721 0.106646 H 4.280882 0.060231 0.453383 C 3.407231 0.305794 3.225409 H 2.819169 0.667692 4.078279 H 4.45 7724 0.283457 3.539782 H 3.324516 1.045440 2.424424 C 0.239764 2.696357 1.440469 H 0.665599 2.716910 2.061057 O 1.348241 3.213405 2.225916 C 1.363757 4.490968 2.692591 O 2.298659 4.850802 3. 368986 C 0.203222 5.397772 2.325448 H 0.756296 4.977899 2.646405 H 0.145596 5.546754 1.241229 H 0.358319 6.361071 2.811886 H 2.328357 0.277038 0.370759 H 0.072268 3.328405 0.566225 TS9 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3755303200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6039860700 a.u Ru 0.703235 0.358680 0.029174 O 2.769469 3.704749 0.619484 O 1.057489 2.507499 0.019681 N 1.721838 2.272126 0.532791 N 0.435299 2.617768 0.389421 C 0.533838 1.645769 0.350166 C 1.638400 3.732393 0.493761 C 2.957052 1.499559 0.418786 C 3.483954 1.499446 1.041930 C 4.736638 0.607958 1.148749 C 5.831083 1.160004 0.212257 C 5.312604 1.164450 1.240854 C 4.063578 2.064981 1.339977 C 4.938562 0.270383 1.654345 C 3.836759 0.830544 0.714722 C 2.587984 0.060520 0.849472 C 4.364 717 0.829205 0.734954 C 1.843086 2.464868 0.637408 C 2.757210 2.848758 0.360712 C 4.127228 2.741448 0.089757 C 2.298189 3.411563 1.686134 C 0.136013 3.951262 0.694788 C 2.293505 2.069789 1.9 16840 C 4.605138 2.289983 1.142075 C 3.669971 1.975512 2.135486 C 1.331903 1.783676 3.049900 C 6.084979 2.136721 1.401118 H 2.266845 0.080010 1.909771 H 2.242352 4.194019 1.278994 H 1.985679 4.114682 0.476341 H 2.693963 1.131588 1.710246 H 3.720447 2.528614 1.349064 H 5.098046 0.617925 2.185479 H 6.116579 2.177016 0.517405 H 6.734098 0.539552 0.283998 H 6.088732 1.558061 1.910251 H 3.697157 2.103984 2.374727 H 4.323616 3.091594 1.042882 H 4.588671 0.288691 2.695672 H 5.823030 0.919776 1.604316 H 3.620871 1.846472 1.039735 H 3.608583 1.244622 1.410539 H 5.242972 1.4 83409 0.809143 H 4.836414 3.020398 0.866033 H 1.367593 2.950268 2.026626 H 3.059868 3.267884 2.458270 H 2.116122 4.492895 1.614136 H 0.280972 4.712366 0.030403 H 0.105291 4.231134 1.728256 H 4.022339 1.648685 3.111190 H 0.761352 2.678653 3.329653 H 1.877062 1.452169 3.938213 H 0.602965 1.008416 2.793830

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118 H 6.378334 1.079546 1.376881 H 6.360872 2.524944 2.388125 H 6.680748 2.664102 0.649442 C 1.158355 0.920158 0.613672 H 1.676170 0.196441 1.237675 N 2.055954 3.309851 0.305982 O 2.194887 3.655388 1.487010 C 1.260936 0.829431 3.932926 C 0.116666 1.198827 2.924615 C 1.9 80927 1.796938 1.787046 C 2.563461 1.226892 3.120244 H 1.157898 1.540760 4.762868 H 3.017739 2.087536 3.628184 C 0.707432 2.483989 2.317987 H 0.070929 2.931300 1.560650 H 0.940629 3.231911 3 .085372 C 0.150017 0.182665 1.773088 C 1.451889 0.627229 0.903355 H 0.862896 1.290707 3.404138 H 2.697282 2.427274 1.253101 H 0.223326 0.849879 2.115187 C 3.668638 0.173933 2.996187 H 4.085830 0.070319 3.980256 H 4.489123 0.556135 2.376844 H 3.328754 0.763272 2.546161 C 1.216208 0.566417 4.562034 H 0.242034 0.738697 5.036910 H 1.980184 0.665182 5.342185 H 1.382913 1.376044 3.8456 62 C 1.412081 2.307017 1.174694 H 0.822155 2.453041 2.085017 O 2.828238 2.343149 1.494437 C 3.401995 3.437829 2.065099 O 4.580690 3.400167 2.330945 C 2.522027 4.644926 2.327516 H 1.688992 4.399534 2.995202 H 2.085614 5.028548 1.398656 H 3.136513 5.420468 2.785344 H 2.116007 0.235333 0.889011 H 1.161708 3.102041 0.475634 9 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3928509300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6141567400 a.u Ru 0.672871 0.476651 0.106072 O 0.815482 1.901641 2.201232 O 1.048083 2.651235 0.171658 N 1.947817 2.072890 0.459081 N 0.175765 2.600165 0.3 81053 C 0.702462 1.549432 0.353240 C 1.988489 3.532516 0.363387 C 3.102786 1.178840 0.354655 C 3.588377 1.047788 1.112506 C 4.723116 0.007912 1.193831 C 5.902231 0.474532 0.316258 C 5.428796 0.619592 1.144735 C 4.293099 1.666098 1.216565 C 4.919936 0.746266 1.647692 C 3.726584 1.219700 0.775810 C 2.605302 0.173151 0.915809 C 4.193425 1.350236 0.688964 C 1.580461 2.561457 0.681062 C 2.498927 2.991096 0.294186 C 3.862009 2.989136 0.024854 C 2.046667 3.481176 1.650547 C 0.518947 3.888608 0.617708 C 2.012476 2.207822 1.977940 C 4.327411 2.596702 1.282100 C 3.383534 2.2 26691 2.247210 C 1.038327 1.803006 3.061213 C 5.805221 2.553644 1.590449 H 2.383577 0.027319 1.980847 H 2.664547 3.968375 1.103628 H 2.323118 3.847352 0.635158 H 2.749619 0.744868 1.749049 H 3.941264 2.024711 1.474190 H 5.053084 0.084701 2.237091 H 6.295151 1.432173 0.686856 H 6.724989 0.250768 0.371713 H 6.263104 0.960024 1.771949 H 3.963032 1.805365 2.254649 H 4.664027 2.636538 0.854353 H 4.610219 0.676862 2.698906 H 5.732775 1.484602 1.602428 H 3.396473 2.195277 1.140496 H 3.360638 1.692808 1.315910 H 4.983659 2.109852 0.761274 H 4.576790 3.303172 0.732744 H 1.190846 2.912781 2.025935 H 2.858119 3.409975 2.380864 H 1.742082 4.536317 1.612371 H 0.141267 4.663632 0.053821 H 0.346086 4.217294 1.650955 H 3.724060 1.941723 3.240342 H 0.216374 2.520793 3.166676 H 1.547771 1.736943 4.027056 H 0.582267 0.827808 2.855378 H 6.197265 1.534968 1.475006 H 6.008854 2.864538 2.621056 H 6.375103 3.204071 0.919025 C 1.345642 0.808966 0.397383 H 1.832 209 0.012940 0.954650 N 1.069132 2.890406 1.447789 O 1.318123 4.010995 1.867467 C 0.685538 0.828917 4.096180 C 0.234817 1.262145 2.907046 C 1.839089 1.645750 2.079120 C 2.134357 1.066351 3.4 98491

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119 H 0.526621 1.574932 4.886577 H 2.592137 1.891316 4.059808 C 0.565552 2.462661 2.368874 H 0.118165 2.936911 1.498527 H 0.734102 3.227672 3.136670 C 0.137658 0.211595 1.786131 C 1.356514 0.517864 1.122129 H 1.264218 1.469143 3.219701 H 2.691677 2.194307 1.671547 H 0.170300 0.812183 2.163006 C 3.126431 0.098427 3.568470 H 3.367364 0.342913 4.609696 H 4.064170 0.170376 3.067436 H 2.753018 1.013822 3.100725 C 0.401296 0.533957 4.736303 H 0.644244 0.590242 5.064912 H 1.029752 0.685309 5.621653 H 0.582555 1.379274 4.065124 C 1.859051 2.140314 0.901621 H 1.545848 2.2 76103 1.939270 O 3.307806 2.071672 0.833399 C 4.092884 3.056538 1.350872 O 5.293227 2.940406 1.269882 C 3.408667 4.242932 2.003160 H 2.832223 3.934066 2.882382 H 2.711190 4.735731 1.317410 H 4.178291 4.951319 2.310582 H 1.906399 0.415858 1.233402 H 1.505792 2.984597 0.306420 TS10 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3903181100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6081479700 a.u Ru 0.581144 0.495855 0.181019 O 0.453473 1.442754 2.333562 O 0.772117 2.702167 0.596377 N 2.022981 1.987760 0.450716 N 0.076537 2.603217 0.322878 C 0.757601 1.515023 0.339442 C 2.124394 3.443273 0.340005 C 3.149299 1.051588 0.384081 C 3.696315 0.931994 1.060249 C 4.788658 0.153897 1.115180 C 5.945826 0.242454 0.176731 C 5.412134 0.379085 1.264211 C 4.319911 1.475763 1.305154 C 4.8 28722 0.979297 1.710122 C 3.651915 1.376447 0.780625 C 2.574015 0.281428 0.907707 C 4.178333 1.497699 0.664258 C 1.487822 2.623419 0.586940 C 2.364841 3.055136 0.425008 C 3.734876 3.113065 0 .143299 C 1.860624 3.486337 1.783205 C 0.664972 3.865959 0.550005 C 1.966212 2.321348 1.880615 C 4.246282 2.778178 1.112621 C 3.342169 2.400675 2.112305 C 1.037550 1.903722 2.998052 C 5.731713 2.806091 1.384581 H 2.382757 0.131333 1.978806 H 2.798673 3.859546 1.093347 H 2.499202 3.732124 0.651869 H 2.876589 0.678252 1.739539 H 4.107933 1.899125 1.384761 H 5.161570 0.239469 2.144829 H 6.395504 1.188933 0.509690 H 6.738055 0.517486 0.211123 H 6.230647 0.670700 1.935473 H 3.949626 1.611522 2.329980 H 4.752923 2.434029 0.980330 H 4.480916 0.923481 2.750100 H 5.61654 2 1.745480 1.677197 H 3.251077 2.343088 1.101499 H 3.362628 1.788277 1.338031 H 4.938612 2.289232 0.719162 H 4.417914 3.430257 0.928422 H 1.008426 2.885068 2.113660 H 2.652476 3.410375 2.534 495 H 1.529396 4.534048 1.771884 H 0.336512 4.641329 0.146902 H 0.481199 4.224698 1.571335 H 3.718580 2.160062 3.104385 H 0.174161 2.572738 3.089554 H 1.566348 1.910434 3.955836 H 0.640865 0.894155 2.841318 H 6.165489 1.802401 1.288526 H 5.946250 3.156262 2.400304 H 6.256988 3.459738 0.680675 C 1.584022 0.758583 0.282106 H 1.988849 0.089273 0.825381 N 0.669206 2.621693 1.880074 O 0.761238 3.602078 2.598756 C 0.281499 0.963414 4.075305 C 0.497665 1.398802 2.792146 C 1.691585 1.652408 2.168631 C 1.792529 1.112061 3.628926 H 0.081636 1.744117 4.821405 H 2.224874 1.936 453 4.210256 C 0.417390 2.517097 2.263852 H 0.087180 2.949115 1.321265 H 0.536820 3.326178 2.995395 C 0.507231 0.301593 1.731113 C 1.417241 0.537872 1.140525 H 1.523975 1.715699 3.018684 H 2.596041 2.198388 1.882133 H 0.520754 0.699206 2.176171 C 2.714659 0.091742 3.849354

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120 H 2.824777 0.305031 4.918766 H 3.714517 0.116449 3.450142 H 2.353906 1.008992 3.374502 C 0.134579 0.360426 4.725565 H 1.213086 0.364612 4.927666 H 0.376905 0.498521 5.685112 H 0.090071 1.239319 4.113194 C 2.140888 2.061489 0.804502 H 1.937512 2.147275 1.874628 O 3.576245 2.007619 0.586322 C 4.410294 2.959111 1.089705 O 5.593941 2.867080 0.863383 C 3.801040 4.077796 1.913214 H 3.335623 3.689497 2.826127 H 3.023932 4.614922 1.358762 H 4.597779 4.770417 2.185532 H 1.705423 0.466519 1.435108 H 1.729086 2.932392 0.291477 10 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3945343300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6085980200 a.u Ru 0.549809 0.486225 0.078724 O 0.177384 1.504609 2.139647 O 0.460771 2.741386 0.379095 N 2.259077 1.757696 0.738202 N 0.224131 2.571299 0.721796 C 0.957698 1.431263 0.523136 C 2.484750 3.191640 0.920646 C 3.300832 0.751725 0.522918 C 3.95823 3 0.914585 0.871406 C 4.936486 0.245332 1.131672 C 6.047207 0.216308 0.063448 C 5.411730 0.360861 1.334228 C 4.432573 0.815864 1.580478 C 4.669666 1.714546 1.398876 C 3.533768 1.742736 0.341 284 C 2.567083 0.594310 0.695758 C 4.158406 1.575570 1.057681 C 1.197343 2.671523 0.885367 C 1.955773 3.302062 0.118622 C 3.336261 3.436118 0.068322 C 1.305805 3.860486 1.363339 C 1.060780 3.694379 1.198427 C 1.801295 2.240837 2.085815 C 3.972032 2.983410 1.227332 C 3.183179 2.403962 2.227483 C 0.999501 1.613798 3.204090 C 5.468881 3.099349 1.393101 H 2.364505 0.683497 1.773535 H 3.172125 3.389366 1.748014 H 2.907932 3.638749 0.010084 H 3.190941 0.937095 1.648573 H 4.492130 1.875483 0.916600 H 5.380636 0.126991 2.129352 H 6.612349 0.724220 0.132901 H 6.762135 1.032 350 0.235220 H 6.196218 0.331529 2.101822 H 3.999743 0.751948 2.587279 H 4.983465 1.766616 1.517644 H 4.251305 1.875109 2.401098 H 5.383782 2.530365 1.216411 H 3.008141 2.701774 0.396525 H 3.374751 1.595880 1.825441 H 4.834492 2.416266 1.267296 H 3.927083 3.910790 0.712281 H 0.521568 3.200354 1.744787 H 2.045937 4.015611 2.154310 H 0.836790 4.834589 1.167030 H 0.818673 4.615789 0.661873 H 0.884637 3.867280 2.268392 H 3.656196 2.068483 3.148089 H 0.112297 2.205621 3.456850 H 1.609910 1.528787 4.108227 H 0.648041 0.609255 2.945114 H 5.966897 2.161290 1.115534 H 5.741 438 3.315181 2.431936 H 5.883186 3.891010 0.760326 C 2.062548 0.765022 0.118194 H 2.194978 0.009247 0.885869 N 0.278634 2.689570 1.652447 O 0.193984 3.692903 2.339065 C 0.318297 0.260928 4.0 71568 C 0.421478 1.021448 2.905714 C 1.891780 1.229753 2.400330 C 1.855830 0.437172 3.742280 H 0.117433 0.850235 4.975484 H 2.257888 1.130710 4.491824 C 0.612065 2.091654 2.527668 H 0.356840 2.651986 1.629543 H 0.736677 2.807070 3.351521 C 0.829444 0.145558 1.739418 C 1.850482 0.348861 1.161648 H 1.352957 1.464571 3.295455 H 2.794671 1.850160 2.348839 H 1.316488 0.768317 2.105202 C 2.736967 0.815454 3.812705 H 2.757100 1.220340 4.830826 H 3.769139 0.569468 3.536278 H 2.402162 1.620069 3.150996 C 0.162794 1.161434 4.376778 H 1.243825 1.173083 4.563442 H 0.326372 1.5 48481 5.277707 H 0.040288 1.868127 3.566349 C 2.525904 2.147365 0.494547 H 2.209811 2.393383 1.510618 O 3.974335 2.112993 0.435717 C 4.724231 3.167366 0.865326

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121 O 5.927031 3.087006 0.786397 C 4.000081 4.380611 1.417283 H 3.417741 4.129017 2.310597 H 3.300901 4.801129 0.686107 H 4.747404 5.130997 1.676276 H 1.781991 0.722218 1.312167 H 2.149199 2.911192 0.189115 TS11 B3LYP/SDD/6 31G(d) S CF energy in gas p hase: 1998.3928341300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6021139200 a.u Ru 0.677478 0.454612 0.229203 O 0.368766 1.094678 2.115556 O 0.249642 2.579699 0.533662 N 2.876764 1.202195 1.020936 N 1.102321 2.501265 0.988376 C 1.539954 1.233272 0.753554 C 3.436515 2.531991 1.271690 C 3.626070 0.025633 0.571195 C 4.206454 0.246423 0.849204 C 4.868153 1.048863 1.358171 C 6.0 06084 1.449358 0.398691 C 5.429097 1.673517 1.014189 C 4.783892 0.358690 1.520691 C 4.377189 2.804508 0.948944 C 3.219906 2.394537 0.003530 C 2.595237 1.121668 0.585388 C 3.801228 2.161467 1 .411703 C 0.261839 2.944851 0.951501 C 0.682436 3.739151 0.135019 C 2.015664 4.156853 0.180634 C 0.282920 4.183653 1.209563 C 2.165953 3.351719 1.560645 C 1.137270 2.650577 2.015238 C 2.927668 3.829760 0.828929 C 2.462168 3.095458 1.923023 C 0.693381 1.898941 3.249213 C 4.374131 4.256863 0.740787 H 2.367275 1.332507 1.649384 H 4.133313 2.526076 2.114779 H 3.970398 2.907814 0.3873 62 H 3.401751 0.552254 1.525482 H 4.944904 1.060677 0.824752 H 5.275786 0.875540 2.363054 H 6.775816 0.664914 0.376714 H 6.494968 2.366663 0.753512 H 6.235171 1.960252 1.701968 H 4.396714 0.485582 2.540124 H 5.544458 0.435512 1.554369 H 3.982168 3.017931 1.950972 H 4.851675 3.728312 0.589324 H 2.467709 3.191421 0.033013 H 3.003719 1.883926 2.110604 H 4.248199 3.092926 1.785706 H 2.347376 4.762008 1.021832 H 0.946743 3.374578 1.526066 H 0.254876 4.550228 2.088840 H 0.919386 5.006661 0.855850 H 2.176619 4.338564 1.090868 H 2.000726 3.486952 2.637989 H 3.144714 2.86 8436 2.739665 H 0.369244 2.046369 3.463015 H 1.263289 2.236641 4.121151 H 0.852222 0.821247 3.144901 H 4.994652 3.458071 0.314075 H 4.783961 4.489515 1.729527 H 4.494271 5.140300 0.105029 C 3.130693 0.703953 0.220913 H 3.232737 0.010646 0.594390 N 0.674293 2.284700 1.701219 O 1.327450 3.053053 2.383697 C 0.514614 0.130920 3.881976 C 0.242006 0.735438 2.784278 C 2.136197 1.194211 2.529014 C 2.019109 0.345899 3.825770 H 0.115640 0.184872 4.854080 H 2.146050 1.061372 4.649354 C 0.750335 1.881760 2.499297 H 0.551069 2.419362 1.574107 H 0.710211 2.607618 3.323057 C 0.78 0485 0.009289 1.572011 C 2.406452 0.361251 1.296647 H 1.155439 1.140300 3.254283 H 2.929392 1.943443 2.640431 H 1.228118 0.959816 1.896613 C 3.100681 0.724596 4.006090 H 3.015875 1.218089 4. 981330 H 4.095337 0.266079 3.955691 H 3.060291 1.499870 3.234624 C 0.305019 1.646561 3.808308 H 0.757384 1.904279 3.895418 H 0.825411 2.145520 4.633190 H 0.675935 2.078271 2.873731 C 3.809375 2.018398 0.028022 H 3.237019 2.601776 0.756839 O 5.123271 1.729102 0.549266 C 5.848006 2.667795 1.217604 O 6.953048 2.372572 1.606748 C 5.221248 4.031556 1.443947 H 4.344343 3.961659 2.097940 H 4.892266 4.490005 0.504904 H 5.968701 4.669294 1.916623 H 1.964537 0.634173 1.280427 H 3.901798 2.616376 0.885982 11 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.396565340 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6012533200 a.u

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122 Ru 0.792449 0.318823 0.533452 O 0.687012 0.590155 1.864243 O 0.831260 1.561507 1.611643 N 3.538441 0.488614 0.288329 N 2.335769 2.312031 0.032150 C 2.266165 0.971383 0.247668 C 4.542175 1.490723 0.078396 C 3.721627 0.964397 0.235445 C 3.926226 1.444334 1.224380 C 3.984862 2.983670 1.268656 C 5.160980 3.472640 0.399733 C 4.956528 2.997405 1.05384 0 C 4.915563 1.450352 1.088627 C 3.631314 3.582691 1.591186 C 2.444361 3.081259 0.724999 C 2.417586 1.548499 0.815207 C 2.657005 3.551760 0.727768 C 1.252163 3.249803 0.131058 C 0.772261 3.857830 1.044740 C 0.270786 4.782728 0.938548 C 1.383941 3.566769 2.395084 C 3.732709 2.796197 0.029268 C 0.743173 3.608085 1.394101 C 0.829895 5.127813 0.295851 C 0.297498 4.541144 1.447278 C 1.288527 3.021616 2.675273 C 1.983213 6.100049 0.381943 H 2.406768 1.285995 1.903006 H 5.401050 1.470934 0.598854 H 4.908541 1.320699 1.100194 H 3.098766 1.074838 1.839896 H 4.856795 1.021 996 1.629731 H 4.132675 3.309059 2.307030 H 6.110985 3.087489 0.796732 H 5.223694 4.568744 0.430224 H 5.791451 3.343857 1.676724 H 4.800469 1.090684 2.119898 H 5.864653 1.046555 0.705585 H 3.482329 3.289238 2.639127 H 3.677997 4.680515 1.571250 H 1.504682 3.488186 1.117975 H 1.821471 3.219719 1.354462 H 2.675509 4.649767 0.765642 H 0.651776 5.248725 1.845045 H 1.632263 2.508203 2.510159 H 0.699703 3.848466 3.200856 H 2.311755 4.136735 2.545232 H 3.908333 3.479143 0.806078 H 3.942761 3.336301 0.961894 H 0.700407 4.816475 2.419568 H 2.379093 2.920812 2.655176 H 1.025573 3.656169 3.527296 H 0.865693 2.028593 2.858710 H 2.945718 5.575298 0.320888 H 1.973921 6.650259 1.328826 H 1.957254 6.828237 0.435806 C 3.988615 0.342033 0.207205 H 4.057103 0.585385 0.772709 N 1.296446 0.519161 2.184153 O 2.221027 0.536555 2.967687 C 1.175608 0.670794 3.312147 C 0.352037 1.346345 2.124222 C 2.761085 1.620277 1.646296 C 2.637825 1.211811 3.140505 H 0.78 6773 1.075219 4.255420 H 2.678004 2.158878 3.697675 C 1.374068 2.258461 1.397465 H 1.152390 2.398458 0.341072 H 1.368598 3.248260 1.872447 C 0.494218 0.402099 1.283587 C 3.046335 0.451227 0. 738625 H 0.411349 1.988823 2.594813 H 3.548255 2.374437 1.534792 H 1.023970 0.304253 1.936885 C 3.770401 0.331039 3.673830 H 3.644990 0.122391 4.743263 H 4.734619 0.837432 3.547764 H 3.836615 0.625962 3.147009 C 1.052288 0.855963 3.431744 H 0.026704 1.146196 3.682105 H 1.693740 1.228785 4.237326 H 1.327633 1.384433 2.513107 C 4.961367 1.393492 0.644353 H 4.756673 1.660201 1.68865 0 O 6.289927 0.832240 0.534111 C 7.375728 1.469960 1.043798 O 8.465237 0.965984 0.903954 C 7.158146 2.785813 1.770196 H 6.548439 2.644157 2.669849 H 6.643011 3.517981 1.138685 H 8.133864 3. 177960 2.058021 H 2.394052 0.411282 0.866333 H 4.893108 2.302097 0.037575 TS12 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.39639722000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.60142585000 a.u Ru 0.857192 0.302121 0.549781 O 0.356043 0.948585 1.871509 O 0.890651 1.155112 1.783213 N 3.681759 0.061203 0.079150 N 2.842151 1.957705 0.159786 C 2.528609 0.662630 0.111491 C 4.824862 0.712747 0.412044 C 3.572694 1.522886 0.073117 C 3.568681 2.070862 1.376728 C 3.322145 3.592055 1.364142 C 4.442003 4.282058 0.559610

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123 C 4.445013 3.738727 0.884368 C 4.710440 2.213378 0.859646 C 3.075271 4.03 7035 1.533801 C 1.947362 3.331570 0.733688 C 2.228361 1.821531 0.769073 C 1.952916 3.869588 0.711342 C 1.978560 3.094251 0.001684 C 1.536185 3.777840 1.146544 C 0.712984 4.895769 0.980728 C 1.956543 3.352008 2.533951 C 4.303155 2.154012 0.275564 C 1.653641 3.555156 1.292357 C 0.336211 5.354722 0.284893 C 0.830097 4.679604 1.404743 C 2.164294 2.877289 2.542691 C 0.588734 6.539087 0.440594 H 2.357611 1.540799 1.844214 H 5.724953 0.531693 0.182578 H 5.047455 0.458031 1.457510 H 2.784614 1.563139 1.949171 H 4.530210 1.850246 1.861819 H 3.324522 3.966332 2.396546 H 5.416107 4.103654 1.036769 H 4.286022 5.369220 0.549899 H 5.240685 4.227639 1.461407 H 4.747392 1.810832 1.880734 H 5.688370 2.016176 0.395466 H 3.065845 3.694304 2.577440 H 2.905124 5.122651 1.553013 H 0.979037 3.537562 1.205748 H 1.155358 3.391527 1.291376 H 1.750474 4.949588 0.707971 H 0.358767 5.421360 1.865104 H 1.947045 2.263922 2.645956 H 1.292693 3.781893 3.289978 H 2.97 4988 3.692154 2.768460 H 4.547604 2.782423 1.135890 H 4.686220 2.646907 0.627949 H 0.568914 5.036114 2.398917 H 3.190594 2.512375 2.430400 H 2.145184 3.572588 3.387832 H 1.533362 2.020926 2. 804110 H 1.628673 6.211060 0.568446 H 0.329048 7.138512 1.320096 H 0.557760 7.192279 0.437771 C 4.387946 0.153674 0.550477 H 4.415688 0.689478 1.238081 N 1.126006 0.013214 2.308534 O 1.978656 0.181388 3.145734 C 1.552424 0.221309 2.941085 C 0.682300 1.131608 1.965820 C 3.088376 1.323588 1.327286 C 2.998229 0.786988 2.785516 H 1.225087 0.412941 3.971329 H 3.039132 1.685849 3.41930 8 C 1.698150 1.981877 1.146654 H 1.421793 2.083382 0.098423 H 1.737816 2.992193 1.572041 C 0.423753 0.391448 1.235582 C 3.356892 0.255500 0.298418 H 0.119437 1.823485 2.614973 H 3.873655 2. 085443 1.273679 H 1.037006 0.157050 1.966580 C 4.145215 0.127672 3.221124 H 4.023778 0.449925 4.262597 H 5.103250 0.400650 3.148383 H 4.222096 1.021216 2.594306 C 1.419201 1.296344 2.732850 H 0.405562 1.632547 2.969263 H 2.099705 1.833418 3.402306 H 1.634931 1.616860 1.709740 C 5.533322 1.106591 0.706019 H 5.543937 1.505772 1.728376 O 6.753066 0.366573 0.464047 C 7.974341 0.90842 9 0.711424 O 8.960945 0.254062 0.469708 C 8.032332 2.312469 1.288371 H 7.587056 2.345718 2.289391 H 7.490268 3.032195 0.665294 H 9.079971 2.606815 1.355343 H 2.601167 0.525219 0.228123 H 5.471163 1.949092 0.010395 12 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.40314080000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.60551951000 a.u Ru 1.144553 0.324785 0.753227 O 1.330899 1.226542 2.263982 O 0.325273 0.156329 2.515810 N 3.354594 1.539187 0.625346 N 3.584628 0.636778 0.865425 C 2.800430 0.331723 0.322809 C 4.474062 1.427261 1.565257 C 2.517806 2.729733 0.440191 C 1.768300 3.081004 1.751158 C 0.800154 4.254216 1.508737 C 1.598102 5.483234 1.029291 C 2.338440 5.134878 0.278455 C 3.321942 3.967633 0.017449 C 1.299847 4.734810 1.350636 C 0.507305 3.487312 0.875586 C 1.515 271 2.346227 0.670189 C 0.225758 3.837112 0.435287 C 3.494926 2.048748 0.612252 C 3.017053 2.890020 1.636405 C 2.963397 4.265784 1.397101 C 2.582467 2.342519 2.975987 C 4.809296 0.071793 1.471250

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124 C 3.952521 2.578307 0.608839 C 3.378033 4.822104 0.182389 C 3.878966 3.962940 0.798249 C 4.505922 1.706729 1.712499 C 3.275279 6.308951 0.065367 H 2.106084 2.261086 1.616607 H 5.3130 64 2.066331 1.275230 H 4.161238 1.709957 2.579765 H 1.217841 2.199025 2.097461 H 2.491640 3.349450 2.533987 H 0.281022 4.493262 2.446477 H 2.315881 5.793401 1.801942 H 0.921740 6.332381 0.86 2554 H 2.907993 6.007275 0.624393 H 3.883078 3.724213 0.929407 H 4.054118 4.266927 0.747302 H 1.799935 4.520825 2.305004 H 0.613790 5.574278 1.531741 H 0.220191 3.200656 1.644726 H 0.805767 2.975023 0.785252 H 0.936069 4.656228 0.255946 H 2.591323 4.920017 2.182745 H 1.815299 1.568966 2.869219 H 2.173285 3.140205 3.603185 H 3.418242 1.890810 3.526052 H 5.014026 0.528503 2.443088 H 5.671027 0.260384 0.817249 H 4.226750 4.377846 1.742006 H 5.048639 0.837295 1.328580 H 5.192317 2.280166 2.343757 H 3.697164 1.336724 2.352081 H 2.318183 6.563399 0.539467 H 4.070276 6.66 0855 0.731514 H 3.337275 6.877089 0.868929 C 5.683334 0.767192 1.322202 H 6.027422 1.361205 2.167149 N 0.304511 0.853213 2.984298 O 0.000432 1.426226 4.005717 C 1.885507 1.447866 1.430597 C 1.358820 0.055625 0.950443 C 3.723013 0.242583 0.245618 C 3.416376 1.196847 1.471117 H 1.520364 1.654723 2.446237 H 3.592028 0.586058 2.368048 C 2.334211 0.326192 0.179612 H 2.017326 0.122301 1.123023 H 2.366554 1.407140 0.351006 C 0.137778 0.002793 0.746715 C 4.418881 0.917544 0.906309 H 1.546390 0.633744 1.795749 H 4.357806 0.568665 0.616259 H 0.641994 0.240132 1.695382 C 4.310012 2.433298 1.592385 H 4.077160 2.989355 2.509002 H 5.367040 2.147455 1.629638 H 4.192521 3.117427 0.746315 C 1.442697 2.607778 0.526913 H 0.350911 2.694908 0.511927 H 1.848951 3.559617 0.885901 H 1.771682 2.479193 0.510509 C 6.721725 0.129872 0.719614 H 7.263604 0.662206 1.510602 O 7.647441 0.701731 0.024258 C 8.800628 0.197035 0.539722 O 9.519021 0.927030 1.180091 C 9.127 282 1.261970 0.272486 H 9.283901 1.441308 0.797501 H 8.321623 1.927356 0.601392 H 10.042968 1.506956 0.811092 H 3.802748 1.622679 1.465723 H 6.280840 0.872452 0.047220 TS13 B3LYP/SDD/6 31G(d) SCF ener gy in gas p hase: 1998.3722343600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.5980442900 a.u Ru 0.613047 0.394410 0.112070 O 2.237797 3.054917 1.293395 O 0.954737 2.505679 0.413654 N 1.758008 2.205191 0.6 95737 N 0.371684 2.649648 0.476580 C 0.557062 1.638287 0.430158 C 1.727409 3.668690 0.755773 C 2.981511 1.409804 0.596138 C 3.627374 1.577003 0.803566 C 4.872075 0.676407 0.918294 C 5.893478 1.078471 0.164804 C 5.254879 0.911542 1.559002 C 4.017448 1.829216 1.667855 C 4.829141 0.556790 1.752125 C 3.792947 0.958038 0.668639 C 2.552783 0.054321 0.820445 C 4.439752 0.789065 0.721816 C 1.798743 2.544127 0.594358 C 2.599526 2.990049 0.474754 C 3.991138 2.936812 0.336908 C 1.984705 3.554287 1.734871 C 0.228157 3.932427 0.910716 C 2.383407 2.135387 1.811838 C 4.601306 2.4 74742 0.832646 C 3.778488 2.093474 1.897740 C 1.551685 1.797741 3.030691 C 6.104224 2.377429 0.945994 H 2.203022 0.138608 1.878838 H 2.314232 4.051942 1.594173 H 2.129909 4.100251 0.171000 H 2.890000 1.307896 1.569287 H 3.904103 2.629689 0.961314 H 5.318829 0.805296 1.913283

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125 H 6.218339 2.118733 0.017108 H 6.790467 0.449741 0.087456 H 5.977836 1.197534 2.334450 H 3.564868 1.751095 2.665927 H 4.324688 2.876160 1.527119 H 4.401680 0.700152 2.754290 H 5.708872 1.211630 1.685023 H 3.526931 2.003343 0.830414 H 3.730126 1.091077 1.497610 H 5.310808 1.452814 0.806657 H 4.6 12582 3.266244 1.166737 H 1.127023 2.964480 2.070863 H 2.718659 3.592432 2.545141 H 1.623996 4.579897 1.577460 H 0.131890 4.759661 0.293567 H 0.048169 4.138078 1.953225 H 4.234443 1.756545 2 .826197 H 1.216515 2.709594 3.543394 H 2.139945 1.221582 3.751243 H 0.656072 1.220396 2.784926 H 6.441979 1.344469 0.792196 H 6.451686 2.684938 1.938468 H 6.604793 3.003516 0.200485 C 1.498670 0.998949 0.616269 H 1.790408 0.238593 1.335216 N 1.849764 3.301503 0.142258 O 2.226167 4.267778 0.522710 C 0.905810 0.751892 3.890020 C 0.097041 1.244859 2.787279 C 1.996537 1.655621 1.852853 C 2.325232 1.000115 3.232275 H 0.800362 1.476365 4.707861 H 2.811728 1.793763 3.813572 C 0.698008 2.414985 2.190604 H 0.216099 2.872338 1.335914 H 0.883735 3.186805 2.947718 C 0.35513 4 0.186236 1.737224 C 1.726715 0.656942 0.732637 H 1.058962 1.557273 3.213459 H 2.809818 2.318580 1.530490 H 0.372406 0.830086 2.149988 C 3.308722 0.173629 3.215478 H 3.569052 0.477357 4.235 990 H 4.238562 0.115559 2.710912 H 2.920593 1.058016 2.703324 C 0.652419 0.624556 4.513556 H 0.381739 0.698552 4.872408 H 1.308627 0.781341 5.377441 H 0.825510 1.456832 3.825120 C 1.689556 2.397545 1.159498 H 1.065191 2.561032 2.041741 O 3.092198 2.474818 1.523648 C 3.612190 3.587140 2.113111 O 4.785229 3.590596 2.403871 C 2.682351 4.757978 2.368437 H 1.868099 4.481609 3.047449 H 2.219549 5.115196 1.442087 H 3.265654 5.563076 2.815858 H 2.054591 0.362806 0.895370 H 1.449910 3.167982 0.428080 TS9E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3719562100 a.u. M06/SDD/6 311++G(d,p) SCF en ergy in solution: 1997.5920563800 a.u Ru 0.687427 0.331237 0.664553 O 1.405400 2.453185 0.219477 O 1.339303 1.746865 2.268428 N 1.798387 1.061436 1.616982 N 0.358606 0.973694 2.034882 C 0.610687 0.618826 1.118890 C 1.719462 1.588948 2.980833 C 3.057618 0.589980 1.023900 C 3.565816 0.676517 1.764078 C 4.849234 1.202707 1.089488 C 5.935345 0.110182 1.115224 C 5.423622 1.132845 0.358957 C 4.163901 1.670184 1.078077 C 5.091013 0.740184 1.098637 C 3.978783 0.345506 1.115378 C 2.734263 0.283229 0.446956 C 4.523542 1.583083 0.367206 C 1.660118 0.396035 2.230448 C 1.750336 0.910 972 2.760213 C 3.015248 1.426873 3.056630 C 0.516452 1.737688 3.045057 C 0.205491 1.715559 3.187840 C 2.815906 1.182588 2.063277 C 4.184516 0.679767 2.873447 C 4.059071 0.623719 2.388503 C 2.769576 2.599521 1.535414 C 5.539328 1.270559 3.185308 H 2.612913 1.261514 0.932445 H 2.236191 2.549489 3.064039 H 2.180168 0.894303 3.695557 H 2.788115 1.447058 1.739990 H 3.774247 0.439794 2.817604 H 5.201908 2.088094 1.634764 H 6.189253 0.154825 2.151961 H 6.855602 0.483983 0.646391 H 6.195894 1.913656 0.364471 H 3.802599 2.587871 0.593678 H 4.421071 1.927117 2.117074 H 4.765 857 1.624395 1.664313 H 5.997930 0.362246 1.591794 H 3.747040 0.612089 2.152489 H 3.809388 2.408266 0.378858 H 5.432895 1.939968 0.870876 H 3.086608 2.433619 3.462688

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126 H 0.176248 1.211004 3.7 13339 H 0.043072 1.979676 2.135164 H 0.790188 2.679454 3.529728 H 0.136829 1.273151 4.127764 H 0.127916 2.760629 3.167934 H 4.952339 1.231713 2.261298 H 3.633459 3.169189 1.891951 H 2.803858 2.621091 0.438495 H 1.865394 3.131364 1.844006 H 5.925625 1.840608 2.330156 H 6.273255 0.491859 3.417027 H 5.490484 1.957594 4.036993 N 1.595194 2.717313 1.465748 O 1.994802 3.801253 1.851622 C 0.016110 1.109596 1.653262 H 0.081246 0.968551 2.742652 C 0.344852 2.520522 1.285675 H 0.559647 2.633719 0.220905 H 0.554619 3.111505 1.520870 O 1.472232 2.992389 2.058739 C 1.750982 4.3 18848 2.209541 O 2.748663 4.634336 2.810741 C 0.776788 5.324369 1.622863 H 0.602033 5.150218 0.555773 H 0.194186 5.272202 2.129162 H 1.195634 6.320751 1.765511 C 3.206115 2.638951 1.815441 C 1.644494 2.437394 1.861331 C 2.414310 0.407097 2.497411 C 3.743306 1.213830 2.246316 H 3.445228 3.345742 2.620698 H 4.216207 1.315434 3.231672 C 1.537789 1.520065 3.099522 H 0.518132 1.220144 3.333004 H 1.988035 1.967681 3.992419 C 1.304694 1.482028 0.717615 C 1.770861 0.213043 1.124356 H 1.086168 3.376155 1.883841 H 2.560806 0.503473 3.081547 H 1.361153 1.809015 0.313157 H 2.1 47746 0.515641 0.420320 C 4.764791 0.534672 1.329641 H 5.693353 1.115493 1.278511 H 5.021030 0.458197 1.719674 H 4.400432 0.406802 0.305883 C 3.761901 3.235734 0.519320 H 3.280068 4.199008 0 .309919 H 4.839361 3.421662 0.603331 H 3.604855 2.590006 0.350165 5E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3875752100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6122282400 a.u Ru 0.744692 0.388458 0.6 47315 O 1.638308 2.507567 0.016790 O 1.516815 1.875324 2.092776 N 1.690693 1.350934 1.434134 N 0.462310 1.222760 1.845561 C 0.531773 0.783008 1.002239 C 1.544384 2.246318 2.582649 C 2.986736 0.862358 0.960202 C 3.589991 0.139790 1.981492 C 4.925582 0.697532 1.449393 C 5.913492 0.460891 1.206003 C 5.313420 1.438059 0.175013 C 3.995653 2.017773 0.734909 C 5.037989 0.686486 1.144549 C 4.030342 0.471901 0.894899 C 2.733407 0.166011 0.378623 C 4.655422 1.444607 0.130326 C 1.734890 0.608942 2.124465 C 1.761131 0.623384 2.817672 C 2.998116 1.137800 3.214418 C 0.493753 1.3 78960 3.149069 C 0.067395 2.056945 2.952482 C 2.922238 1.324950 1.885402 C 4.199234 0.461968 2.968273 C 4.135717 0.768299 2.312061 C 2.941727 2.662785 1.181095 C 5.522427 1.056637 3.388568 H 2.414633 0.939494 1.118454 H 1.773754 3.280584 2.298886 H 2.219916 1.964505 3.397120 H 2.876859 0.955873 2.144070 H 3.750960 0.362942 2.945814 H 5.343424 1.391298 2.190400 H 6.126635 0.987415 2.147260 H 6.869566 0.066533 0.836927 H 6.015346 2.262185 0.007956 H 3.565903 2.748360 0.035980 H 4.193254 2.545743 1.679367 H 4.642546 1.378092 1.901236 H 5.976184 0.278493 1.544699 H 3.840223 0.988898 1.839740 H 3.992316 2.294481 0.309697 H 5.594928 1.843058 0.276179 H 3.021991 2.087410 3.744604 H 0.208578 0.765985 3.727610 H 0.036181 1.706541 2.248274 H 0.723331 2.267062 3.745067 H 0.063593 1.533280 3.906688 H 0.479384 3.002761 3.014381 H 5.054585 1.320744 2.127398 H 3.791301 3.263257 1.521456 H 3.049550 2.538278 0.096497 H 2.028156 3.238316 1.353990 H 5.882 932 1.776224 2.641857 H 6.292220 0.286085 3.498588 H 5.437373 1.592879 4.340054

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127 N 1.858674 2.788517 1.244671 O 2.365452 3.837951 1.603840 C 0.400359 0.732194 1.862415 H 0.159570 0.513608 2.9 10754 C 0.659246 2.205354 1.693485 H 0.796960 2.473724 0.643133 H 0.191799 2.768829 2.093298 O 1.866937 2.565042 2.423269 C 2.197903 3.856227 2.688204 O 3.245100 4.089147 3.244514 C 1.218575 4.943833 2.280298 H 0.959489 4.883822 1.217710 H 0.285889 4.864585 2.850830 H 1.680249 5.909160 2.489386 C 2.873975 2.983967 1.314515 C 1.342386 2.677414 1.457585 C 2.301268 0.928925 2.527610 C 3.537106 1.724439 2.008700 H 3.058168 3.852647 1.960887 H 4.064985 2.075904 2.905276 C 1.339494 2.075413 2.881431 H 0.358372 1.755183 3.227937 H 1.761694 2.761596 3.624979 C 1.008434 1.4 81922 0.553884 C 1.556030 0.234845 1.346469 H 0.724320 3.564171 1.291479 H 2.545141 0.220280 3.324238 H 1.383927 1.570480 0.461130 H 2.199752 0.358134 0.696241 C 4.553619 0.924281 1.189370 H 5.440483 1.529760 0.967143 H 4.888160 0.045402 1.754150 H 4.153681 0.572876 0.233872 C 3.373444 3.373087 0.079202 H 2.797352 4.224889 0.462235 H 4.425453 3.681575 0.041928 H 3.296156 2.564523 0.811157 TS10E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.3675764300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution : 1997.6001314700 a.u Ru 0.799578 0.530272 0.161577 O 3.152847 2.728310 2.369822 O 1.487698 2.40898 6 0.990751 N 1.480321 1.842046 1.305639 N 0.715187 1.950127 1.262615 C 0.370541 1.226047 0.813710 C 1.215958 3.108793 1.990604 C 2.785508 1.519875 0.723193 C 3.022791 2.381454 0.549354 C 4. 359874 1.998407 1.209274 C 5.505623 2.243312 0.205813 C 5.277422 1.388918 1.058829 C 3.939293 1.782486 1.718992 C 5.226015 0.097167 0.664831 C 4.071023 0.346097 0.341965 C 2.742329 0.032609 0.335910 C 4.307280 0.510300 1.601906 C 2.020327 2.112191 0.670673 C 2.120056 2.818901 0.551610 C 3.388742 3.115413 1.055317 C 0.896501 3.324661 1.282330 C 0.300874 3.043722 2.179851 C 3.179237 1.787511 1.402562 C 4.559319 2.767581 0.370919 C 4.427731 2.119821 0.857026 C 3.149447 1.110903 2.754826 C 5.918273 3.080987 0.950063 H 2.617468 0.576957 1.261592 H 1.754647 3.165746 2.939987 H 1.525538 3.961190 1.370343 H 2.193793 2.215854 1.249005 H 3.023798 3.448164 0.284548 H 4.511061 2.619799 2.101816 H 5.557384 3.309301 0.058463 H 6.468610 1.980824 0.663128 H 6.091 736 1.561500 1.774577 H 3.774954 1.199555 2.635440 H 3.963610 2.843944 2.005404 H 5.088954 0.726754 1.554223 H 6.176445 0.399730 0.204893 H 4.097230 1.397579 0.605068 H 3.509188 0.328486 2.3 32587 H 5.248762 0.209301 2.079124 H 3.464018 3.656914 1.995879 H 0.326654 4.033038 0.666908 H 0.208918 2.519907 1.558635 H 1.187203 3.846745 2.198408 H 0.808482 3.973915 1.913390 H 0.573139 2.791579 3.211686 H 5.322231 1.865571 1.421590 H 3.967583 1.482782 3.380509 H 3.280403 0.025912 2.665087 H 2.213615 1.284422 3.291582 H 6.224430 2.310021 1.669271 H 6.686152 3.124452 0.171085 H 5.917000 4.038421 1.482536 N 2.672524 2.911494 1.247315 O 3.226624 3.567096 0.355829 C 0.490153 1.757236 0.783077 H 0.174648 2.785629 0.591881 C 0.875515 1.541148 2.226656 H 1.039149 0.4 87354 2.441979 H 0.086837 1.910126 2.889253 O 2.141083 2.173541 2.543502 C 2.245603 3.461584 2.982255 O 3.350811 3.925575 3.127086 C 0.972796 4.226480 3.295868

PAGE 135

128 H 0.432031 3.764365 4.130063 H 0.290879 4.268425 2.440614 H 1.257042 5.239930 3.579855 C 2.372171 1.113926 3.256248 C 0.911152 1.353190 2.739274 C 2.162546 2.353655 1.141390 C 3.243320 1.757570 2.097060 H 2.474232 1.755823 4.141150 H 3.765914 2.626527 2.518269 C 1.087603 2.771233 2.155551 H 0.182769 3.184732 1.722692 H 1.481878 3.473322 2.900005 C 0.695474 0.447061 1.514615 C 1.462205 1.223004 0.315291 H 0.151289 1.236214 3.517088 H 2.558427 3.138149 0.489089 H 1.086816 0.558383 1.650773 H 2.158089 0.533015 0.159840 C 4.314380 0.875368 1.453799 H 5.085533 0.606282 2.185567 H 4.811615 1.412021 0.636270 H 3.916807 0.056270 1.044660 C 2.734124 0.301757 3.713758 H 2.019296 0.648472 4.470986 H 3.728714 0.317034 4.175626 H 2.745277 1.035123 2.902701 6E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1 998.3850188400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.614248 a.u Ru 0.802659 0.477815 0.231870 O 2.126075 3.010517 0.749879 O 1.647101 2.188545 1.242029 N 1.595542 1.824204 1.307907 N 0.590446 1.980616 1.406620 C 0.441985 1.254009 0.864610 C 1.404336 3.068802 2.057701 C 2.861842 1.480713 0.651324 C 3.062408 2.362145 0.612889 C 4.343318 1.938616 1.354899 C 5.553412 2.109136 0.413940 C 5.359452 1.230907 0.840363 C 4.079091 1.670778 1.585936 C 5.232217 0.244455 0.410994 C 4.010396 0.419391 0.528596 C 2.752870 0.002689 0.249706 C 4.206113 0.463693 1.778186 C 1.947975 2.11 6350 0.945779 C 2.180102 2.882045 0.222351 C 3.497187 3.118897 0.619259 C 1.043841 3.512726 0.997325 C 0.103365 3.039084 2.326565 C 3.025835 1.683479 1.740273 C 4.590908 2.647868 0.119063 C 4.330138 1.947871 1.295770 C 2.857109 0.982065 3.069771 C 6.004847 2.892980 0.351217 H 2.670582 0.608286 1.170928 H 1.993928 3.072187 2.978230 H 1.705985 3.936643 1.455361 H 2.188902 2.247370 1.268109 H 3.123856 3.421965 0.327650 H 4.471957 2.573724 2.241332 H 5.664127 3.164637 0.126921 H 6.477269 1.820910 0.932549 H 6.218973 1.350911 1.512444 H 3.939885 1.073706 2.496999 H 4.172863 2.722952 1.892402 H 5.122102 0.892356 1.290437 H 6.147330 0.562478 0.107371 H 3.943585 1.463333 0.835213 H 3.356263 0.338704 2.461889 H 5.104649 0.142758 2.322074 H 3.675842 3.705316 1.517976 H 0.503377 4.246565 0.384945 H 0.306582 2.780568 1.338890 H 1.426197 4.039866 1.876117 H 0.599218 3.988897 2.110348 H 0.331135 2.766469 3.364097 H 5.163102 1.603005 1.904972 H 3.506 377 1.442903 3.822969 H 3.141575 0.074510 3.001447 H 1.830338 1.028692 3.438915 H 6.304624 2.144192 1.095999 H 6.718914 2.835285 0.476385 H 6.106051 3.877099 0.821939 N 2.196401 3.119412 0.4 95322 O 2.757199 4.049763 1.067060 C 0.562013 1.775112 0.499273 H 0.298909 2.794783 0.214702 C 0.937412 1.697147 1.955675 H 1.111210 0.670223 2.265035 H 0.132574 2.113385 2.567151 O 2.188227 2.379663 2.224093 C 2.247358 3.706863 2.539936 O 3.336253 4.221727 2.630900 C 0.949710 4.449471 2.804431 H 0.472027 4.073049 3.717174 H 0.221716 4.350719 1.993329 H 1.195333 5.502036 2.947795 C 2.209432 0.654195 3.515325 C 0.778501 0.959593 2.954016 C 2.111245 2.124665 1.546867 C 3.139126 1.431410 2.492826 H 2.264640 1.178411 4.478699 H 3.625274 2.248213 3.042487 C 0.974513 2.4 30675 2.536115 H 0.087635 2.881015 2.099912

PAGE 136

129 H 1.316224 3.055199 3.370022 C 0.611261 0.200917 1.627339 C 1.466877 1.097577 0.559870 H 0.017868 0.760759 3.678402 H 2.537941 2.977681 1.010154 H 0.987643 0.818683 1.670575 H 2.185702 0.453433 0.054436 C 4.260013 0.640096 1.814048 H 4.991429 0.290873 2.552962 H 4.794495 1.277403 1.098947 H 3.901650 0.238070 1.270770 C 2.550608 0.810428 3.805647 H 1.789366 1.256821 4.458270 H 3.511676 0.887370 4.328097 H 2.624370 1.427312 2.905575 TS11E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.383921110 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.6039824400 a.u Ru 0.596339 0.492715 0.266095 O 0.353520 0.971950 2.557623 O 1.111226 2.486437 1.199134 N 1.706597 2.145713 0.066071 N 0.429769 2.462631 0.426335 C 0.503518 1.520072 0.072389 C 1.677215 3.506024 0.604751 C 2.927330 1.381440 0.202949 C 3.619474 0.941131 1.110411 C 4.822757 0.034363 0.787027 C 5.837299 0.826234 0.062457 C 5.159768 1.287326 1.369209 C 3.953811 2.196 179 1.030901 C 4.687906 0.044518 2.153480 C 3.655499 0.749247 1.310829 C 2.453984 0.182069 1.051854 C 4.326805 1.198798 0.002895 C 1.837796 2.446959 0.146260 C 2.749171 2.431023 1.217466 C 4.118323 2.489464 0.930888 C 2.282052 2.392583 2.653825 C 0.174688 3.806822 0.591510 C 2.284676 2.588608 1.184898 C 4.596093 2.599667 0.377709 C 3.660896 2.663974 1.417266 C 1.320361 2.624383 2.348433 C 6.078368 2.624076 0.666748 H 2.137997 0.594873 2.020334 H 2.254090 4.198080 0.014683 H 2.094772 3.527194 1.620764 H 2.899785 0.409262 1.740289 H 3.955326 1.827609 1.668334 H 5.296 752 0.284490 1.725181 H 6.208320 1.693452 0.502573 H 6.709009 0.199412 0.293687 H 5.874753 1.860423 1.974141 H 3.477635 2.561320 1.950506 H 4.305566 3.074567 0.469353 H 4.238904 0.343804 3.1 09911 H 5.553007 0.590503 2.391710 H 3.338793 1.631966 1.873538 H 3.618526 1.777009 0.608583 H 5.173640 1.862711 0.219913 H 4.827576 2.456307 1.755141 H 2.016929 3.397073 3.012030 H 1.395068 1.765022 2.777552 H 3.071374 2.015506 3.311160 H 0.179295 4.277360 1.512713 H 0.111108 4.450320 0.250221 H 4.012811 2.764992 2.441805 H 0.542561 3.386278 2.220725 H 1.850973 2.846026 3.279133 H 0.805191 1.665058 2.473856 H 6.452669 1.612716 0.872085 H 6.305590 3.239832 1.543608 H 6.646983 3.016581 0.182615 N 0.779349 2.171233 2.405146 O 0.856939 2.966383 3.326274 C 1.380181 1.428399 0.344585 H 1.190311 2.427726 0.739670 C 2.506131 0.741261 1.071626 H 2.781910 0.190029 0.587325 H 2.247626 0.543329 2.112922 O 3.701138 1.562496 0.994053 C 4.043097 2.462236 1.957723 O 5.002368 3.171286 1.761547 C 3.233027 2.506885 3.242138 H 3.318139 1.563412 3.793852 H 2.167240 2.686992 3.070295 H 3.637050 3.311481 3.856985 C 0.304015 2.016637 3.823611 C 1.000910 1.98 7423 2.426160 C 1.133796 2.622832 1.911437 C 1.185702 2.397740 3.453669 H 0.739352 2.874297 4.353700 H 1.387030 3.387906 3.882449 C 0.295542 3.162388 1.726288 H 0.589957 3.309986 0.688814 H 0.441586 4.105724 2.266660 C 0.652650 0.728528 1.639879 C 1.251244 1.325481 1.085475 H 2.091072 2.092089 2.504426 H 1.921474 3.310451 1.582199 H 0.475445 0.131770 2.295304 H 1.828784 0.517632 1.528676 C 2.296215 1.476530 3.968922 H 2.334518 1.488902 5.064111 H 3.273297 1.813502 3.601950 H 2.170281 0.433626 3.663240

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130 C 0.517467 0.803125 4.734427 H 1.589273 0.610860 4.869570 H 0.09 1499 0.985222 5.727822 H 0.062078 0.116618 4.353900 7E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.403191120 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.606685860 a.u Ru 1.010958 0.318363 0.723289 O 0.736338 0.177452 2.023951 O 0.392343 2.032313 2.126717 N 2.743350 1.854134 0.013081 N 0.694712 2.525215 0.450808 C 1.433280 1.484985 0.016223 C 2.957916 3.137079 0.687472 C 3.753557 0.809059 0.1733 72 C 4.220260 0.238212 1.190512 C 5.188806 0.939319 0.964743 C 6.413979 0.449523 0.166896 C 5.947424 0.113488 1.191366 C 4.993429 1.308436 0.950668 C 5.224853 1.003064 1.977771 C 3.983422 1.489255 1.181795 C 3.047474 0.284524 1.000567 C 4.454799 2.043178 0.177715 C 0.737003 2.650441 0.408071 C 1.458546 2.588115 1.616405 C 2.847082 2.742112 1.572728 C 0.764944 2.400159 2.946073 C 1.531764 3.715814 0.713097 C 1.387492 2.919844 0.811016 C 3.532369 2.971114 0.374271 C 2.779418 3.067319 0.800185 C 0.629792 3.062376 2.111053 C 5.036450 3.103791 0.353162 H 2.872707 0.14 8984 2.018733 H 3.660265 3.771486 0.139041 H 3.354151 2.982996 1.700732 H 3.344353 0.095113 1.758444 H 4.715876 1.026307 1.775043 H 5.513599 1.330295 1.938156 H 6.952550 0.322834 0.734168 H 7.117160 1.278065 0.007647 H 6.815999 0.463465 1.764209 H 4.675923 1.747887 1.905713 H 5.520421 2.093857 0.388541 H 4.917192 0.635434 2.966026 H 5.916462 1.839602 2.150186 H 3.465407 2.273623 1.746842 H 3.596778 2.406523 0.754340 H 5.124271 2.899913 0.018915 H 3.409569 2.686328 2.502293 H 0.281481 3.327536 3.283790 H 0.012723 1.631847 2.898131 H 1.482829 2.112090 3.719448 H 1.27 1794 4.173977 1.670608 H 1.375544 4.462369 0.076743 H 3.287792 3.272881 1.739854 H 0.313819 3.604096 1.984464 H 1.232178 3.606197 2.845428 H 0.393917 2.081659 2.537159 H 5.517083 2.122417 0. 257055 H 5.369711 3.716734 0.491322 H 5.408278 3.565034 1.274777 N 0.602212 1.361098 2.566438 O 1.369950 1.762886 3.412738 C 3.613220 2.089229 0.283119 H 4.187991 3.009745 0.169244 C 4.157155 1.041544 1.209530 H 3.405155 0.273632 1.397963 H 4.453000 1.468499 2.172780 O 5.275090 0.312776 0.630015 C 6.567153 0.686031 0.780249 O 7.425911 0.014476 0.253085 C 6.882389 1.911840 1.62092 4 H 6.621891 1.743396 2.672259 H 6.334718 2.796996 1.282403 H 7.954194 2.098827 1.549805 C 0.025119 2.580410 2.897137 C 0.606754 2.419892 1.455436 C 1.789704 2.978867 1.230245 C 1.531166 2.543228 2.728817 H 0.273586 3.617476 3.166060 H 1.958049 3.317012 3.379482 C 0.376322 3.315780 0.667398 H 0.307970 3.198507 0.413503 H 0.139615 4.362801 0.897228 C 0.796218 0.979985 0.981848 C 2.457298 1.937837 0.372264 H 1.609002 2.876392 1.431476 H 2.418376 3.877081 1.215140 H 0.825727 0.274271 1.821161 H 1.913460 1.004353 0.233289 C 2.203350 1.221660 3.128226 H 2.057963 1.01 8476 4.195433 H 3.281693 1.268708 2.942231 H 1.816816 0.364063 2.568517 C 0.614895 1.705377 4.006923 H 1.706610 1.810383 4.043664 H 0.223754 2.010832 4.985087 H 0.385953 0.642334 3.886796 TS12 E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.40264906000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.60547016000 a.u Ru 1.092487 0.207023 0.839665 O 0.507623 0.076108 2.287826 O 0.621869 1.774257 2.432735

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131 N 2.747400 1.840503 0.320446 N 0.669778 2.461881 0.682282 C 1.444434 1.486780 0.137608 C 2.902240 3.015846 1.181479 C 3.775940 0.825570 0.075882 C 4.140227 0.076190 1.382869 C 5.127236 1.0675 69 1.076226 C 6.407909 0.484534 0.445735 C 6.044724 0.257605 0.856974 C 5.069028 1.415424 0.533832 C 5.389954 0.740709 1.837669 C 4.093666 1.319648 1.209865 C 3.141940 0.145036 0.940025 C 4 .460015 2.052678 0.096097 C 0.752417 2.611579 0.544643 C 1.562686 2.420080 1.683712 C 2.941153 2.603338 1.560657 C 0.968773 2.064679 3.027315 C 1.481665 3.603797 1.156262 C 1.307985 3.033537 0.676582 C 3.533113 2.992029 0.351808 C 2.696992 3.207853 0.746109 C 0.464179 3.310331 1.899882 C 5.029579 3.173456 0.252402 H 3.042221 0.422342 1.901152 H 3.653512 3.708943 0.792351 H 3.201680 2.717621 2.195823 H 3.224859 0.322804 1.834173 H 4.588844 0.776063 2.102026 H 5.378507 1.586110 2.011035 H 6.899847 0.200774 1.150435 H 7.123513 1.289637 0.230943 H 6.953122 0.676342 1.309338 H 4.821840 1.977499 1.444426 H 5.548543 2.118169 0.163801 H 5.157018 0.243215 2.788875 H 6.096557 1.550819 2.066330 H 3.624455 2.018303 1.913274 H 3.560884 2.482203 0.551758 H 5.14 2087 2.885895 0.122724 H 3.571772 2.446163 2.433120 H 0.504375 2.938467 3.505302 H 0.194404 1.295974 2.944876 H 1.742794 1.699451 3.708397 H 1.141594 3.948756 2.135828 H 1.393565 4.439726 0. 449215 H 3.132460 3.533962 1.688372 H 0.531836 3.684640 1.643050 H 0.950876 4.056534 2.536372 H 0.331306 2.401396 2.496632 H 5.547703 2.209770 0.323785 H 5.312025 3.637694 0.698060 H 5.406991 3.808391 1.062922 N 0.317972 1.055265 2.918878 O 0.985041 1.371143 3.878080 C 3.839711 1.942626 0.269326 H 4.409128 2.873046 0.245522 C 4.470184 0.771365 0.960952 H 3.772670 0.067821 1.00409 0 H 4.761991 1.019412 1.987102 O 5.618490 0.249837 0.239640 C 6.887689 0.681505 0.451397 O 7.779986 0.184326 0.195865 C 7.131310 1.747482 1.506506 H 6.920426 1.360043 2.510096 H 6.506716 2. 633490 1.356270 H 8.182697 2.031479 1.454693 C 0.104908 3.029647 2.363786 C 0.541045 2.605933 0.926618 C 1.888531 3.077821 0.859429 C 1.459983 2.934144 2.375055 H 0.339968 4.103132 2.409404 H 1.843559 3.809910 2.913712 C 0.556043 3.313937 0.092972 H 0.592614 2.985113 0.944729 H 0.330830 4.388334 0.083013 C 0.696752 1.100382 0.717735 C 2.618592 1.897951 0.273765 H 1.511125 3.06575 2 0.690403 H 2.538508 3.953938 0.749415 H 0.541374 0.516205 1.633173 H 2.071630 0.955544 0.233025 C 2.044849 1.703724 3.083623 H 1.773755 1.699268 4.145497 H 3.138369 1.710050 3.019345 H 1.701068 0.760828 2.647470 C 0.839579 2.385991 3.543380 H 1.922012 2.541119 3.454129 H 0.520903 2.837750 4.490699 H 0.664129 1.308756 3.624009 8E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1998.41105643000 a .u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1997.61330911000 a.u Ru 1.472062 0.071703 1.026378 O 0.393965 0.906336 2.721174 O 1.188311 1.102039 2.947861 N 2.954197 1.546182 0.953492 N 0.912348 2.371062 0.955072 C 1.717255 1.436818 0.385696 C 2.970170 2.475714 2.088071 C 3.858207 0.400482 0.791848 C 3.672966 0.609553 1.953406 C 4.535391 1.862392 1.706140 C 6.017970 1.448217 1.614749 C 6.201 808 0.448916 0.453808 C 5.345261 0.812626 0.720202 C 5.763708 1.124146 0.864939

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132 C 4.267727 1.529053 0.776794 C 3.445985 0.252311 0.543799 C 4.090344 2.523780 0.386162 C 0.446137 2.661762 0.587458 C 1.481569 2.251183 1.452659 C 2.804899 2.495385 1.075271 C 1.192452 1.586714 2.779664 C 1.660024 3.254259 1.872125 C 0.727528 3.376039 0.590899 C 3.121708 3.161340 0.115333 C 2.0693 32 3.604364 0.920473 C 0.361761 3.895389 1.501000 C 4.562425 3.421919 0.489694 H 3.725745 0.468726 1.354441 H 3.852144 3.122476 2.070396 H 2.964244 1.929787 3.041611 H 2.614097 0.883929 2.02 0697 H 3.959478 0.143062 2.906550 H 4.398492 2.564871 2.539185 H 6.343661 0.994764 2.561868 H 6.648576 2.332600 1.450920 H 7.256944 0.153658 0.384190 H 5.483034 1.549999 0.081798 H 5.668060 1.286746 1.659213 H 5.919596 0.442120 1.711935 H 6.386289 2.010633 1.051327 H 3.956873 1.997057 1.718910 H 3.040864 2.831652 0.454301 H 4.685114 3.428664 0.198839 H 3.612586 2.153398 1.718869 H 0.837651 2.314000 3.523362 H 0.423598 0.811645 2.699008 H 2.098318 1.129196 3.187605 H 1.103945 3.424158 2.797537 H 1.833661 4.227673 1.393750 H 2.293188 4.143807 1.838742 H 1.281801 4.12 7570 0.955613 H 0.029999 4.808241 2.006917 H 0.610794 3.160401 2.273524 H 5.222382 2.642542 0.095970 H 4.687811 3.469968 1.576786 H 4.906517 4.381531 0.079505 N 0.545032 0.139597 3.493088 O 0.108592 0.170652 4.621727 C 5.202246 2.464496 0.927266 H 5.248478 3.457495 1.376960 C 6.501132 1.701271 0.959941 H 6.791518 1.486739 1.995117 H 7.316209 2.290298 0.520074 O 6.413859 0.410056 0.340127 C 6.545997 0.241796 1.001644 O 6.295575 0.845059 1.472524 C 7.031988 1.412304 1.835187 H 8.052500 1.696575 1.553515 H 6.389301 2.288711 1.705259 H 7.026837 1.105010 2.881121 C 0.653212 3.319224 0.637897 C 0.254037 2.248478 0.440791 C 2.730330 2.705089 0.434501 C 2.148294 3.062591 0.968195 H 0.635415 4.280956 0.104054 H 2.606072 3.995394 1.325754 C 1.623147 1.841023 1.095916 H 1.824905 0.779011 0.914043 H 1.601660 1.969817 2.182347 C 0.441491 0.993157 0.050471 C 4.053460 1.994831 0.434151 H 0.376352 2.724799 1.198075 H 2.829344 3.645850 0.993113 H 0.13 0096 0.661820 1.049130 H 4.043281 0.986424 0.022778 C 2.401339 1.989514 2.036224 H 1.899070 2.243707 2.975813 H 3.471925 1.903433 2.252926 H 2.050229 1.000385 1.726038 C 0.284860 3.469421 1. 838269 H 1.288592 3.763010 1.511820 H 0.079682 4.247442 2.520953 H 0.384606 2.544231 2.415022 TS17 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1626446700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.27446096 00 a.u Ru 0.811303 0.577117 0.394666 O 1.714624 0.076964 2.418236 O 0.408078 0.357952 2.049751 N 2.197073 2.899748 0.586711 N 3.124138 1.195546 1.610935 C 2.174756 1.545093 0.691933 C 3.069497 3.554544 1.562575 C 1.183978 3.569071 0.231639 C 0.022735 4.116397 0.634322 C 1.079595 4.701564 0.271330 C 0.491203 5.852337 1.111852 C 0.665834 5.311814 1.976792 C 1.770694 4.743628 1.05396 3 C 0.122627 4.208343 2.911577 C 0.457259 3.040499 2.066553 C 0.701816 2.486923 1.218433 C 1.608195 3.591280 1.202316 C 3.691335 0.107226 1.816644 C 3.389873 0.805427 2.999357 C 4.017465 2. 036491 3.226814 C 2.427993 0.245377 4.021532 C 3.889416 2.366695 2.094587 C 4.628966 0.614964 0.892090 C 4.941860 2.573622 2.327497 C 5.238598 1.841780 1.171002

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133 C 4.966203 0.124864 0.382771 C 5.590930 3.914369 2.577931 H 1.540533 2.303831 1.911708 H 3.693942 4.321469 1.094571 H 2.478733 4.033506 2.355271 H 0.382167 3.311097 1.254839 H 0.400613 4.892910 1.314888 H 1.896847 5.082455 0.355639 H 0.133180 6.657809 0.455013 H 1.268775 6.287036 1.754509 H 1.090521 6.127009 2.577024 H 2.622473 4.384707 1.646335 H 2.142523 5.540925 0.393335 H 0.920700 3.837379 3.568077 H 0.657539 4.627872 3.562190 H 0.836385 2.259503 2.735175 H 2.058160 2.784602 0.614855 H 2.399171 3.993753 1.850407 H 3.779438 2.585305 4.135380 H 1.509380 0.123586 3.554926 H 2.158896 1.007 910 4.758667 H 2.867836 0.597977 4.570801 H 3.966375 2.354323 3.185528 H 4.906599 2.349258 1.683322 H 5.961061 2.239658 0.461393 H 5.294036 1.153182 0.190394 H 5.772627 0.383591 0.919445 H 4.101746 0.185696 1.053977 H 5.150687 4.689078 1.937265 H 6.664221 3.886306 2.358077 H 5.465023 4.233063 3.617444 C 5.469295 2.581166 0.155322 H 5.564193 3.662689 0.232090 N 0.572061 0.468622 2.871667 O 0.439557 0.930395 3.991970 C 2.426852 0.053057 2.429392 C 1.872065 0.548358 1.100151 C 3.988034 0.623950 0.567777 C 3.933464 0.208078 2.093810 H 2.305997 0.675586 3.243291 H 4.350 681 0.808162 2.132176 C 2.585232 0.258100 0.004532 H 2.017913 1.165599 0.232753 H 2.652791 0.291513 0.946460 C 0.378995 0.774665 1.030693 C 4.330059 2.070189 0.330177 H 2.282641 1.575935 1.0 72157 H 4.752955 0.002209 0.091682 H 0.042972 1.131053 2.022291 C 4.766279 1.066582 3.048628 H 4.725998 0.660264 4.066827 H 5.815053 1.090776 2.734060 H 4.419124 2.104115 3.087126 C 1.730947 1.350401 2.863001 H 0.664842 1.175656 3.046903 H 2.163413 1.737210 3.791803 H 1.809751 2.141774 2.109393 C 6.679539 1.798405 0.573187 H 7.169277 2.287483 1.422798 O 7.592616 1.749310 0.552273 C 8.847213 1.234756 0.430251 O 9.545289 1.172650 1.413786 C 9.303144 0.775712 0.943373 H 9.350760 1.616806 1.644697 H 8.623108 0.030886 1.370910 H 10.298058 0.341785 0.841326 H 3.548799 2.7 82752 0.600342 H 6.418917 0.777577 0.871094 C 0.867516 2.242780 0.450361 C 1.876999 2.507227 0.391120 H 1.050810 1.812001 1.427755 H 0.155830 2.521176 0.213920 H 2.896265 2.257452 0.111937 C 1.718840 3.184893 1.720062 H 2.087508 2.531184 2.515763 H 0.667445 3.426289 1.916911 O 2.508455 4.390423 1.669426 C 2.772652 5.107380 2.799715 O 3.448776 6.103022 2.701499 C 2.201787 4.606055 4.112579 H 2.637435 3.640249 4.392771 H 1.117110 4.464052 4.060431 H 2.437074 5.339893 4.883775 13 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1622957500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2757622400 a.u Ru 0.929807 0.456838 0.463296 O 1.613436 0.135863 2.675108 O 0.486636 0.023039 2.144432 N 2.575313 2.557391 0.648006 N 3.450437 0.708536 1.430906 C 2.455504 1.204570 0.626719 C 3.564287 3.052511 1.606502 C 1.582360 3.390621 0.032801 C 0.516020 3.919916 0.957062 C 0.570772 4.698448 0.189204 C 0.078332 5.891674 0.540744 C 1.142453 5.369623 1.527648 C 2.232730 4.606 521 0.738951 C 0.465630 4.435438 2.555524 C 0.170811 3.223594 1.823036 C 0.971130 2.472088 1.107476 C 1.231775 3.758845 0.840684 C 3.948658 0.636066 1.488656 C 3.760877 1.378766 2.669896 C 4.312015 2.662355 2.746829 C 2.986737 0.815424 3.839908

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134 C 4.352987 1.775884 1.919763 C 4.716684 1.149363 0.423016 C 5.049070 3.214976 1.695297 C 5.246592 2.437772 0.548944 C 4.972890 0.344433 0.831891 C 5.601344 4.618060 1.783619 H 1.762135 2.326090 1.858894 H 4.187372 3.839064 1.172058 H 3.070341 3.460997 2.499056 H 0.072832 3.077990 1.499287 H 0.989132 4.574229 1.703703 H 1.324332 5.065124 0.899215 H 0.537487 6.576560 0.186519 H 0.686636 6.465238 1.081082 H 1.608884 6.216236 2.048395 H 3.023957 4.256186 1.414647 H 2.698535 5.287637 0.010980 H 1.198813 4.085649 3.293999 H 0.303391 4.993408 3.108702 H 0.651313 2.566168 2.555407 H 1.732242 2.927237 0.334197 H 2.008164 4.304662 1.395150 H 4.160460 3.244457 3.653344 H 2.028133 0.387465 3.527184 H 2.788 795 1.592969 4.583789 H 3.539610 0.013195 4.346128 H 4.563849 1.649751 2.985061 H 5.307113 1.736759 1.377886 H 5.832965 2.843712 0.272593 H 5.420913 0.630859 0.607554 H 5.658811 0.878872 1.4 95580 H 4.050926 0.147255 1.390582 H 4.915937 5.338424 1.318563 H 6.562102 4.703646 1.264646 H 5.746658 4.927447 2.823823 C 5.598457 2.259611 0.022605 H 5.804482 3.327546 0.018181 N 0.402103 0.022508 3.076253 O 0.113166 0.180508 4.250306 C 2.280126 0.013092 2.512292 C 1.681546 0.496381 1.164931 C 3.922251 0.442960 0.683251 C 3.799084 0.007480 2.194938 H 2.062971 0.713773 3.307579 H 4.087256 1.068256 2.204640 C 2.500098 0.236707 0.079631 H 2.039850 1.204632 0.148373 H 2.523153 0.309648 0.864875 C 0.177372 0.579851 1.051117 C 4.412071 1.853510 0.493764 H 1.977032 1.5 61082 1.122984 H 4.628433 0.238901 0.199176 H 0.242783 0.777593 2.053869 C 4.721425 0.712744 3.180983 H 4.627236 0.279682 4.184445 H 5.767503 0.622606 2.869413 H 4.500262 1.782290 3.254709 C 1.744617 1.374595 2.976825 H 0.662125 1.335105 3.143779 H 2.208638 1.671330 3.923121 H 1.941934 2.174767 2.254108 C 6.721990 1.370085 0.423806 H 7.266485 1.839186 1.250781 O 7.615307 1.177345 0.701832 C 8.818572 0.555891 0.558759 O 9.495538 0.373720 1.541992 C 9.246806 0.136101 0.836047 H 9.377012 1.007835 1.487804 H 8.507737 0.519468 1.309385 H 10.197760 0.390497 0.753140 H 3.7 08310 2.633959 0.788166 H 6.356923 0.395814 0.765120 C 0.889174 1.885251 0.605753 C 1.487775 2.021263 0.608748 H 1.460494 1.674397 1.498328 H 0.141115 2.194685 0.746639 H 2.563258 1.908060 0 .688190 C 0.824999 2.739479 1.754362 H 1.146896 2.331225 2.713428 H 0.265908 2.682520 1.682341 O 1.254081 4.117217 1.648352 C 1.033386 5.009616 2.655601 O 1.415887 6.145714 2.509157 C 0.320327 4.519623 3.901639 H 0.917595 3.770444 4.433826 H 0.642789 4.054737 3.664686 H 0.159888 5.376364 4.556505 TS18 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1612070500 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 2343.2772160400 a.u Ru 0.954729 0.479546 0.507474 O 1.591148 0.376916 2.763397 O 0.481703 0.115297 2.177824 N 2.506061 2.526282 0.822551 N 3.407566 0.645311 1.495911 C 2.439431 1.179210 0.683734 C 3.414257 2.967431 1.882521 C 1.513047 3.373508 0.156141 C 0.341230 3.727532 1.104848 C 0.740139 4.506289 0.328605 C 0.127711 5.815656 0.207981 C 1.052878 5.481693 1.1430 48 C 2.129997 4.698902 0.354462 C 0.534464 4.632522 2.323761 C 0.070429 3.306492 1.791240 C 1.048151 2.540652 1.056703 C 1.242720 3.644069 0.848911

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135 C 3.980204 0.669730 1.421146 C 3.835780 1 .540190 2.517449 C 4.439870 2.801032 2.453908 C 3.068421 1.138430 3.757025 C 4.239809 1.698478 2.122807 C 4.766500 1.032050 0.306324 C 5.192423 3.206557 1.348777 C 5.352991 2.301085 0.293887 C 4.969681 0.096370 0.864237 C 5.798597 4.588183 1.282032 H 1.908780 2.495355 1.739726 H 4.025415 3.816631 1.565213 H 2.849655 3.267273 2.776382 H 0.077213 2.808679 1.527422 H 0.709268 4.3345 48 1.944928 H 1.574028 4.738962 1.004734 H 0.212453 6.444677 0.626972 H 0.886134 6.392273 0.754452 H 1.497623 6.411323 1.521871 H 2.991898 4.478214 0.997849 H 2.491717 5.316732 0.481358 H 1 .350347 4.415645 3.025809 H 0.224220 5.201016 2.880616 H 0.443168 2.718176 2.636323 H 1.702292 2.720737 0.477526 H 2.022013 4.188755 1.400408 H 4.316661 3.482831 3.292629 H 2.148318 0.596680 3.515368 H 2.804411 2.018413 4.351269 H 3.664453 0.479474 4.403056 H 4.404969 1.485186 3.182011 H 5.218135 1.742102 1.626587 H 5.951645 2.590341 0.567171 H 5.298795 0.899134 0.544465 H 5.7288 11 0.494446 1.544030 H 4.046419 0.044281 1.438396 H 5.143450 5.275459 0.731318 H 6.764933 4.577294 0.766202 H 5.950051 5.009112 2.281344 C 5.664416 2.342746 0.146175 H 5.906607 3.399529 0.240894 N 0.376097 0.209718 3.137398 O 0.047176 0.133596 4.308833 C 2.289876 0.336338 2.457270 C 1.664945 0.220765 1.141567 C 3.928554 0.618792 0.596833 C 3.803958 0.245340 2.129517 H 2.05658 3 0.344907 3.287916 H 4.054192 0.823548 2.186681 C 2.495026 0.429993 0.013515 H 2.069364 1.402233 0.261768 H 2.490552 0.165479 0.900660 C 0.153748 0.294606 1.041940 C 4.462549 2.001644 0.336 996 H 1.932310 1.292614 1.146528 H 4.607788 0.108266 0.140703 H 0.270530 0.395926 2.052598 C 4.760963 0.976320 3.073607 H 4.656664 0.596507 4.097479 H 5.800241 0.829610 2.761526 H 4.582279 2.056118 3.095813 C 1.810590 1.735833 2.868447 H 0.733422 1.742013 3.067964 H 2.311185 2.058433 3.787080 H 2.012442 2.496609 2.105439 C 6.758805 1.391485 0.535312 H 7.347089 1.812020 1.358109 O 7.609925 1.188859 0.621097 C 8.787178 0.509946 0.531435 O 9.421173 0.317449 1.540988 C 9.242282 0.043330 0.839604 H 9.432671 0.895214 1.502665 H 8.490678 0.588553 1.325248 H 10.165456 0.522 896 0.714477 H 3.782946 2.818076 0.586514 H 6.358755 0.425314 0.860719 C 0.756194 1.598232 0.587346 C 1.489008 1.671273 0.625186 H 1.304012 1.614538 1.521413 H 0.218038 2.075179 0.613265 H 2.568588 1.725649 0.540735 C 0.941270 2.470737 1.781427 H 1.392042 2.144960 2.721956 H 0.146630 2.380558 1.852321 O 1.298940 3.851936 1.524065 C 1.096687 4.824541 2.455223 O 1.408541 5.959486 2.181306 C 0.492609 4.421920 3.787493 H 1.154447 3.739743 4.333084 H 0.466264 3.907960 3.660501 H 0.345579 5.325676 4.379323 14 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1781473200 a.u. M06/SDD/6 311++G( d,p) SCF energy in solution: 2343.3008358100 a.u Ru 1.244299 0.444284 0.526609 O 1.778076 1.020926 3.411422 O 0.051039 0.838367 2.205323 N 3.133503 1.458476 1.433577 N 2.824840 0.614747 2.059067 C 2.472 392 0.312655 1.117586 C 3.811612 1.408807 2.732181 C 2.741109 2.698420 0.762537 C 1.613371 3.411358 1.555446 C 1.129009 4.656740 0.788934 C 2.314362 5.625061 0.598165 C 3.434382 4.918953 0.1 93607 C 3.923112 3.681309 0.594641

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136 C 2.886174 4.481108 1.566976 C 1.697588 3.500228 1.377641 C 2.230464 2.268231 0.623649 C 0.585560 4.213557 0.583302 C 2.560876 2.027266 2.076222 C 1.529847 2.528562 2.892462 C 1.297941 3.910785 2.901908 C 0.706958 1.641492 3.799998 C 3.844814 0.099777 2.998870 C 3.407833 2.906018 1.363899 C 2.074935 4.798470 2.155839 C 3.136205 4.274771 1.407308 C 4.611567 2.412621 0.589458 C 1.784216 6.280604 2.146128 H 3.074482 1.839132 1.196700 H 4.809160 1.853141 2.682968 H 3.232499 1.948286 3.494405 H 0.782863 2.710123 1.706759 H 1.982540 3.7 01047 2.549591 H 0.335985 5.150652 1.365674 H 2.691320 5.960462 1.574813 H 1.984238 6.522404 0.058223 H 4.278732 5.606548 0.332220 H 4.743474 3.182865 0.061486 H 4.310117 3.996026 1.575129 H 3.675122 4.001404 2.160993 H 2.551638 5.362164 2.131956 H 1.327382 3.210829 2.361664 H 0.273896 3.543405 0.455351 H 0.228000 5.085766 1.146854 H 0.488713 4.299657 3.516874 H 0.771953 0.588003 3.521790 H 0.348466 1.934099 3.787927 H 1.050547 1.732558 4.839486 H 3.588191 0.364993 4.028241 H 4.823747 0.537537 2.765564 H 3.767467 4.951210 0.835283 H 5.492190 2.336143 1.241844 H 4.865906 3.111107 0.213403 H 4.449790 1.427846 0.142568 H 1.347862 6.588046 1.187360 H 2.698714 6.868416 2.285601 H 1.079290 6.556666 2.936531 C 6.353732 1.124293 1.547778 H 6.848180 1.422983 2.470769 N 0.531449 1.091492 3.356476 O 0.181518 1.374234 4.313782 C 2.281898 1.266818 0.875793 C 1.753220 0.023655 0.109756 C 4.177960 0.307010 0.468531 C 3.792780 1.229689 0.520645 H 1.83 2726 2.175818 0.454760 H 3.859316 1.581702 0.517367 C 2.813177 1.057595 0.443842 H 2.604415 1.498200 1.428625 H 2.811173 1.883988 0.274668 C 0.322777 0.404891 0.404175 C 5.061444 0.775264 1. 593409 H 1.830401 0.252372 0.958125 H 4.692440 0.480009 0.481464 H 0.178582 0.618297 1.463287 C 4.716966 2.122490 1.352251 H 4.406635 3.171877 1.275826 H 5.751168 2.052047 0.997673 H 4.723190 1.850786 2.412773 C 1.989077 1.258335 2.384575 H 0.910212 1.267170 2.575325 H 2.411865 2.144643 2.869366 H 2.404487 0.378908 2.891695 C 7.242792 1.121981 0.340427 H 7.742326 2.094190 0.235154 O 8.239957 0.093918 0.543677 C 9.229950 0.127239 0.365295 O 10.048309 0.983717 0.132059 C 9.242043 0.714861 1.628248 H 9.340581 1.781885 1.399203 H 8.317800 0.586737 2.202897 H 10.0894 10 0.399081 2.237108 H 4.575370 0.828671 2.569170 H 6.683866 0.924212 0.578697 C 0.197052 1.630187 0.477875 C 1.599587 1.433846 1.156272 H 0.290750 2.479492 0.202679 H 0.541712 1.828698 1.25 6856 H 2.380124 1.969744 0.626134 C 1.669633 1.790529 2.626124 H 2.563112 1.356494 3.082339 H 0.789889 1.449371 3.175069 O 1.744084 3.238597 2.674968 C 1.839363 3.908079 3.856728 O 1.928876 5.113205 3.831106 C 1.820959 3.095288 5.136953 H 2.636465 2.364433 5.162899 H 0.885132 2.534546 5.238980 H 1.922788 3.782308 5.977325 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1709441900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2896575000 a.u Ru 1.268292 0.524196 0.338260 O 0.234425 2.234385 0.714278 O 0.124968 1.809954 1.414250 N 3.805480 0.357963 1.056487 N 3.049668 1.691046 1.1 37017 C 2.743672 0.423888 0.719529 C 4.815898 0.317993 1.874178 C 3.705592 1.811214 0.944484 C 3.301059 2.444813 2.303244

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137 C 3.143890 3.970852 2.151373 C 4.468613 4.584351 1.658869 C 4.843218 3.964338 0.296494 C 5.039577 2.443543 0.473721 C 3.715651 4.230911 0.723539 C 2.385348 3.599280 0.222494 C 2.622514 2.083822 0.104067 C 2.026794 4.252749 1.131247 C 2.248878 2.882465 1.164681 C 1.416294 3.101779 2.287365 C 0.694307 4.292611 2.361641 C 1.318200 2.082834 3.400276 C 4.405551 1.786412 1.721965 C 2.406142 3.875229 0.182284 C 0.786791 5.279026 1.368810 C 1.652384 5.053575 0.299599 C 3.378720 3.751612 0.969664 C 0.032305 6.544597 1.463290 H 2.991838 1.718977 1.093419 H 5.825909 0.122873 1.503277 H 4.764777 0.020697 2.917558 H 2.357175 1.997169 2.638371 H 4.064981 2.219540 3.060501 H 2.875615 4.401488 3.124892 H 5.271496 4.404925 2.388253 H 4.363538 5.672997 1.561014 H 5.781007 4.404711 0.066717 H 5.349875 1.977487 0.471203 H 5.836828 2.25 7619 1.208050 H 3.988108 3.818777 1.705065 H 3.581127 5.312899 0.857957 H 1.599376 3.800041 0.957716 H 1.071421 3.871175 1.497005 H 1.913938 5.336426 0.989373 H 0.045830 4.460115 3.218978 H 0.974658 1.108063 3.037396 H 0.620773 2.421862 4.171724 H 2.289759 1.917575 3.883324 H 4.375781 2.326090 2.672822 H 5.068509 2.336533 1.042146 H 1.760172 5.817763 0.467620 H 4.136089 4.543763 0.916155 H 2.867743 3.862827 1.932977 H 3.896188 2.790552 0.976128 H 1.089002 6.346376 1.242533 H 0.316726 7.302083 0.754828 H 0.010930 6.975073 2.470422 C 6.362864 0.072157 1.154980 H 7.02 2641 0.632416 1.815272 N 0.643124 2.513592 0.451345 O 1.476498 3.375996 0.686958 C 2.515363 1.450806 1.309772 C 1.711291 0.375306 0.511678 C 4.094559 0.007253 0.029453 C 3.913089 0.782738 1. 401166 H 2.092281 1.555479 2.319073 H 3.821428 0.002505 2.168815 C 2.686203 0.021692 0.632908 H 2.659674 0.796904 1.408965 H 2.465418 0.923429 1.130510 C 0.259543 0.765237 0.215260 C 5.152697 0.574694 0.876766 H 1.660610 0.497405 1.174726 H 4.354547 1.026815 0.274681 H 0.088716 1.418435 1.010177 C 5.078665 1.681777 1.821953 H 4.888783 2.119941 2.809867 H 6.010268 1.108639 1.88082 8 H 5.250023 2.503441 1.119080 C 2.522858 2.843328 0.661311 H 1.508531 3.249695 0.588783 H 3.113647 3.547019 1.258132 H 2.950759 2.833953 0.347848 C 6.944139 1.195670 0.604077 H 7.460995 1.751261 1.396155 O 7.897566 0.830548 0.425409 C 8.647287 1.769244 1.064788 O 9.420698 1.409093 1.919968 C 8.467570 3.222921 0.664978 H 8.727463 3.382367 0.387609 H 7.431372 3.552764 0.799339 H 9.122750 3.829063 1.290998 H 4.893082 1.521299 1.354392 H 6.173512 1.844929 0.178508 C 0.118222 1.355242 1.180849 C 1.462673 0.780607 1.830465 H 0.291349 2.425282 1.043215 H 0.692994 1.193 294 1.890418 H 2.258434 1.523071 1.801879 C 1.287546 0.256217 3.238368 H 2.216617 0.218952 3.580896 H 0.475368 0.473078 3.292387 O 1.001610 1.393101 4.094157 C 0.659552 1.241274 5.402196 O 0.459548 2.229979 6.067586 C 0.540454 0.169981 5.947625 H 1.465628 0.739049 5.805044 H 0.261715 0.721746 5.444325 H 0.315539 0.103724 7.012351 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1641768700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2863039800 a.u Ru 1.099236 0.685150 0.519076 O 1.012163 0.675187 3.142885 O 0.325255 1.146651 2.088927 N 2.917914 2.099573 1.243226 N 3.173686 0.004739 1.822477

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138 C 2.504420 0.832276 0.960897 C 3.725727 2.196403 2.461468 C 2.159901 3.214545 0.676415 C 0.976851 3.598625 1.606657 C 0.114344 4.690621 0.945619 C 0.989934 5.932562 0.679029 C 2.161 692 5.550483 0.248953 C 3.030077 4.468169 0.434783 C 1.598398 5.007312 1.578887 C 0.721714 3.754520 1.315160 C 1.619291 2.689661 0.660439 C 0.443116 4.145645 0.383979 C 3.236744 1.431620 1.8 51529 C 2.456312 2.136360 2.789246 C 2.536825 3.534593 2.808623 C 1.591466 1.439475 3.816956 C 4.153237 0.739020 2.653236 C 4.167502 2.111895 1.035794 C 3.389959 4.240985 1.957763 C 4.210543 3.507131 1.093825 C 5.147762 1.381339 0.142486 C 3.429233 5.750804 1.962729 H 2.477251 2.479603 1.333440 H 4.572654 2.875015 2.330878 H 3.119188 2.560211 3.302743 H 0.372456 2.702362 1.802868 H 1.361700 3.953730 2.573046 H 0.710629 4.957064 1.619432 H 1.371471 6.338981 1.626476 H 0.387483 6.723240 0.212565 H 2.783551 6.434377 0.441199 H 3.888303 4.204284 0.197720 H 3.428616 4.8 57363 1.383344 H 2.418909 4.757067 2.265505 H 0.996459 5.783062 2.072233 H 0.323210 3.372180 2.256248 H 1.085659 3.274361 0.204907 H 1.067760 4.906448 0.870846 H 1.919364 4.082330 3.517717 H 1.368394 0.406031 3.544030 H 0.643128 1.968162 3.959145 H 2.096827 1.422827 4.792292 H 4.103513 0.403613 3.692645 H 5.169503 0.555541 2.280928 H 4.904871 4.035001 0.443614 H 6.101459 1.224033 0.664708 H 5.366436 1.968024 0.755257 H 4.781152 0.401815 0.174332 H 2.882290 6.159741 1.103554 H 4.457186 6.124278 1.896723 H 2.974966 6.161310 2.869990 C 5.931439 1.617578 0.955993 H 6.3 58759 2.432425 1.536482 N 1.110071 0.556214 2.956679 O 1.915560 1.264993 3.554777 C 2.082828 1.609752 1.770625 C 1.491697 0.498127 0.842714 C 3.898474 0.738292 0.307396 C 3.586160 1.228480 1 .775882 H 1.678326 1.497549 2.786911 H 3.657813 0.329081 2.403915 C 2.504659 0.415209 0.315147 H 2.265313 1.142680 1.095652 H 2.498550 0.565970 0.794610 C 0.010799 0.619759 0.578168 C 4.666394 1.724490 0.529525 H 1.591779 0.430900 1.427811 H 4.490846 0.178565 0.390857 H 0.489440 0.832925 1.532827 C 4.559697 2.253226 2.362600 H 4.294764 2.485464 3.401861 H 5.581542 1.860294 2.3520 02 H 4.568491 3.192793 1.800658 C 1.785773 3.044125 1.309583 H 0.714385 3.263111 1.370432 H 2.301444 3.771637 1.945292 H 2.100810 3.227396 0.276221 C 6.846792 0.460101 0.671577 H 7.653253 0.426191 1.411556 O 7.409336 0.631326 0.655991 C 8.357046 0.213732 1.143507 O 8.737677 0.062824 2.280437 C 8.892682 1.296296 0.223987 H 9.393279 0.861893 0.648912 H 8.092046 1.945122 0.147753 H 9.610641 1.893653 0.786408 H 4.121527 2.626011 0.812566 H 6.308608 0.493501 0.710148 C 0.610443 1.572146 0.536439 C 1.895127 0.983464 1.270790 H 0.986276 2.449809 0.004208 H 0.142375 1.83 7390 1.275164 H 2.803591 1.350333 0.803919 C 1.981655 1.186410 2.767720 H 2.819707 0.601780 3.171164 H 1.055615 0.903953 3.260173 O 2.269886 2.592459 2.973349 C 1.982445 3.226015 4.145183 O 2.264143 4.397240 4.245197 C 1.323756 2.424321 5.250815 H 1.916602 1.541160 5.514989 H 0.330902 2.072926 4.948799 H 1.230323 3.071019 6.123746 TS23 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1455322800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2648872500 a.u Ru 0.923687 0.560907 0.489840

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139 O 0.796448 1.631685 2.772974 O 0.397479 0.480396 2.238107 N 2.306568 2.605699 1.030277 N 3.116574 0.730515 1.823209 C 2.247608 1.252018 0.902312 C 3.102120 3.054447 2.176904 C 1.271860 3.427703 0.395344 C 0.095906 3.677921 1.378450 C 1.033471 4.445495 0.665922 C 0.487345 5.798343 0.164603 C 0.68 0992 5.552301 0.812932 C 1.814222 4.794600 0.081901 C 0.171832 4.717323 2.007361 C 0.369940 3.352715 1.508220 C 0.777202 2.608155 0.804869 C 1.531974 3.606122 0.527144 C 3.561724 0.625343 1. 997193 C 2.988568 1.418455 3.010550 C 3.463412 2.724909 3.185801 C 1.922792 0.903052 3.953614 C 3.879538 1.782690 2.530054 C 4.657862 1.104317 1.244372 C 4.500521 3.248334 2.411835 C 5.093790 2.413806 1.457743 C 5.393863 0.239511 0.242688 C 4.970387 4.672446 2.591933 H 1.626733 2.532601 1.531555 H 3.753988 3.891102 1.911502 H 2.447977 3.377122 2.998114 H 0.272437 2.711116 1.74416 2 H 0.446097 4.251355 2.248382 H 1.854541 4.618545 1.374600 H 0.150592 6.409180 1.014418 H 1.283482 6.362867 0.338747 H 1.071445 6.514275 1.169973 H 2.667931 4.635980 0.754511 H 2.172962 5. 396779 0.766194 H 0.981569 4.557147 2.732612 H 0.620891 5.268314 2.532973 H 0.723023 2.758471 2.353143 H 1.935711 2.647992 0.175236 H 2.348709 4.131630 1.040997 H 3.013145 3.343657 3.959703 H 1.627597 0.122512 3.723881 H 1.022902 1.528840 3.922383 H 2.287118 0.926576 4.988355 H 3.912326 1.576473 3.603628 H 4.910811 1.811213 2.155839 H 5.919781 2.792884 0.859746 H 6.295914 0.195218 0.694231 H 5.719231 0.833390 0.617452 H 4.781326 0.585602 0.129569 H 4.576306 5.318956 1.797335 H 6.063048 4.741940 2.550667 H 4.638748 5.086320 3.549540 C 5.667904 2.320015 0.969287 H 5.935088 3.209292 1.535729 N 0.946932 0.413109 3.020648 O 1.596672 0.000064 3.977921 C 2.043688 1.597416 1.977895 C 1.575460 0.462332 1.014743 C 3.870354 1.094808 0.356395 C 3.585596 1.461 845 1.868629 H 1.729458 1.368128 3.006213 H 3.842574 0.558993 2.440535 C 2.501509 0.604509 0.206294 H 2.088700 1.344425 0.895997 H 2.591690 0.327523 0.768819 C 0.087051 0.267391 0.868176 C 4.429859 2.221903 0.468849 H 1.854327 0.477044 1.533417 H 4.593871 0.273190 0.354224 H 0.408597 0.486498 1.820310 C 4.417995 2.605268 2.451995 H 4.179953 2.752102 3.513057 H 5.485677 2.379045 2.370993 H 4.244352 3.554101 1.934106 C 1.495049 2.985494 1.619346 H 0.405818 3.018577 1.730664 H 1.911876 3.751302 2.281741 H 1.729016 3.276252 0.589262 C 6.754489 1.295197 0.792125 H 7.565 000 1.476497 1.505502 O 7.265928 1.388393 0.562893 C 8.318378 0.635381 0.982514 O 8.652023 0.703568 2.141864 C 9.022238 0.241209 0.037238 H 9.467190 0.362308 0.836688 H 8.331268 0.948964 0.5 08154 H 9.810902 0.792182 0.475589 H 3.740901 3.041273 0.677288 H 6.375445 0.280128 0.959402 C 1.202072 1.810347 0.365042 C 2.189865 1.125067 1.100885 H 1.459576 2.196583 0.614407 H 0.371810 2.272090 0.886624 H 3.160854 1.022983 0.635082 C 2.282634 1.226635 2.609158 H 1.318601 1.494526 3.032840 H 2.639016 0.289570 3.056050 O 3.272001 2.251535 2.871911 C 3.312246 2.919126 4.059463 C 2.250409 2.602159 5.095357 H 1.247630 2.853290 4.731757 H 2.243523 1.537173 5.353209 H 2.467296 3.188804 5.988405 O 4.187571 3.735030 4.227982

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140 TS19 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1478674200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2681426800 a.u Ru 1.251925 0.406796 0.357217 O 0.842740 2.039405 3.571347 O 0.126818 0.894649 1.954428 N 2.509230 1.302520 2.071565 N 2.573 689 0.884699 2.226147 C 2.196044 0.157976 1.416799 C 2.916102 1.087410 3.461849 C 2.087661 2.583793 1.493130 C 0.675539 2.974380 1.999800 C 0.201985 4.267150 1.307514 C 1.195229 5.402628 1.6 27806 C 2.599503 5.015150 1.120055 C 3.066266 3.727273 1.838363 C 2.538496 4.779796 0.403747 C 1.549627 3.628715 0.727150 C 2.072203 2.348494 0.039473 C 0.148857 4.025502 0.214119 C 2.764744 2.253857 1.833846 C 1.856983 3.235917 2.272517 C 2.057403 4.562317 1.867594 C 0.710886 2.923510 3.208677 C 3.265112 0.406850 3.444535 C 3.915075 2.618484 1.096217 C 3.140104 4.939960 1.071882 C 4.067078 3.953488 0.714054 C 5.016308 1.630574 0.771302 C 3.312254 6.366725 0.606740 H 3.121434 2.220844 0.343879 H 3.764692 1.718789 3.736770 H 2.086416 1.307342 4.148392 H 0.024169 2.1 54984 1.788458 H 0.691911 3.110502 3.091217 H 0.795985 4.532315 1.680989 H 1.220528 5.592836 2.710479 H 0.868182 6.334131 1.147276 H 3.308924 5.822408 1.344795 H 4.080982 3.453775 1.518777 H 3.099278 3.905178 2.924047 H 3.537576 4.536546 0.791149 H 2.218312 5.703283 0.906346 H 1.520583 3.483426 1.810198 H 0.582222 3.243381 0.451199 H 0.191751 4.934998 0.726561 H 1.345191 5.319257 2.190137 H 0.530044 1.850504 3.296899 H 0.216493 3.402322 2.875429 H 0.923961 3.309238 4.214580 H 2.909555 0.944947 4.327643 H 4.346414 0.572706 3.353051 H 4.938427 4.232340 0.125118 H 5.756358 1.598925 1.582699 H 5.551020 1.930607 0.135444 H 4.646395 0.613167 0.625174 H 3.008765 6.477141 0.442303 H 4.358052 6.686601 0.674492 H 2.705750 7.058185 1.200157 C 6.422454 2.028130 1.082033 H 6.923076 2.489402 1.931775 N 0.178715 1.809550 2.896459 O 1.256437 2.370016 3.081533 C 2.333357 0.365844 0.860357 C 1.791261 0.720068 0.105045 C 4.218762 1.111441 0.151537 C 3.83 6409 0.394257 0.471279 H 1.884629 1.337717 0.616833 H 3.878574 0.917806 0.492649 C 2.853482 1.845545 0.008778 H 2.658769 2.463414 0.895658 H 2.825611 2.519770 0.853760 C 0.390285 1.253540 0. 118935 C 5.111922 1.767035 1.171245 H 1.839955 0.305563 1.115042 H 4.725401 1.117796 0.818252 H 0.157378 1.549353 1.137301 C 4.776247 1.135082 1.424799 H 4.467638 2.182585 1.528407 H 5.804926 1.124366 1.048558 H 4.798633 0.689237 2.424463 C 2.074338 0.080974 2.348209 H 1.000535 0.052116 2.564817 H 2.509022 0.865283 2.976595 H 2.503075 0.874025 2.674660 C 7.323299 1.710478 0.07402 6 H 7.907974 2.596414 0.354802 O 8.223205 0.663834 0.360065 C 9.206502 0.186080 0.453542 O 9.947765 0.664941 0.025225 C 9.306043 0.747930 1.860118 H 9.484095 1.829030 1.850379 H 8.384071 0. 572249 2.425898 H 10.135828 0.252182 2.364238 H 4.619035 2.052766 2.102284 H 6.761805 1.378987 0.952222 C 0.354871 1.837568 0.888342 C 2.493155 0.551177 1.325281 H 1.110734 2.580433 0.660317 H 0.033491 1.770787 1.923753 H 3.074172 1.387934 0.928169 C 2.801934 0.276313 2.766316 H 3.777558 0.241750 2.797178 H 2.060683 0.373940 3.230241 O 2.920538 1.551048 3.434573 C 2.932409 1.63876 2 4.798114 O 3.017992 2.734771 5.297698 C 2.840926 0.351754 5.593360

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1 41 H 3.649890 0.338490 5.328538 H 1.898944 0.174606 5.404242 H 2.911576 0.603607 6.651788 15 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1482630200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2690339900 a.u Ru 1.288366 0.347341 0.283864 O 0.953889 2.445375 3.203930 O 0.069675 1.151667 1.738239 N 2.540487 0.775705 2.265913 N 2.450534 1.409282 2.102745 C 2.162050 0.238569 1.454432 C 2.919550 0.335107 3.610963 C 2.231740 2.153083 1.860125 C 0.824502 2.562536 2.363317 C 0.467890 3.971861 1.853021 C 1.514093 4.977152 2.374872 C 2.912761 4.571858 1.866385 C 3.263061 3.164621 2.404661 C 2.908968 4.562733 0.322744 C 1.867389 3.539889 0.202221 C 2.275943 2.140171 0.306636 C 0.471970 3.956287 0.311721 C 2.51 2660 2.720515 1.520025 C 1.517855 3.664545 1.837603 C 1.589205 4.934462 1.251688 C 0.416711 3.374782 2.832923 C 3.160770 1.163974 3.377848 C 3.616441 3.081423 0.714760 C 2.626003 5.295949 0.388861 C 3.637830 4.359204 0.148518 C 4.806936 2.167677 0.513623 C 2.658728 6.655675 0.268451 H 3.330685 1.987794 0.033813 H 3.809577 0.857624 3.969862 H 2.102882 0.514690 4.324305 H 0.0845 22 1.833273 2.004856 H 0.795650 2.534448 3.462586 H 0.528270 4.248880 2.222615 H 1.501776 5.004605 3.473985 H 1.268016 5.989073 2.027237 H 3.660756 5.286959 2.233032 H 4.272159 2.869924 2.08 6230 H 3.256518 3.181586 3.505082 H 3.908910 4.310523 0.056872 H 2.671555 5.568564 0.051382 H 1.874331 3.550382 1.295555 H 0.297553 3.270717 0.060967 H 0.216070 4.951915 0.074220 H 0.811648 5.660026 1.481996 H 0.262917 2.303890 2.980588 H 0.531885 3.819682 2.514257 H 0.659647 3.810317 3.811861 H 2.757948 1.795611 4.174311 H 4.228221 1.393523 3.262627 H 4.474652 4.632934 0.490747 H 5.563983 2.350104 1.288808 H 5.286070 2.358260 0.451794 H 4.541995 1.108975 0.555983 H 2.308483 6.599023 1.307248 H 3.674944 7.064324 0.293273 H 2.017038 7.370350 0.256666 C 6.685390 1.70 4470 0.743477 H 7.225004 2.204272 1.546446 N 0.077665 2.176937 2.561235 O 1.131033 2.799210 2.673942 C 2.405587 0.381406 0.825433 C 1.960696 0.637234 0.257079 C 4.424806 0.794180 0.055525 C 3.888761 0.613832 0.429537 H 1.853018 1.321121 0.697160 H 3.853219 1.240235 0.471276 C 3.140389 1.645633 0.293233 H 3.026629 2.393402 0.503060 H 3.171694 2.199257 1.237331 C 0.635639 1.340220 0.084324 C 5.375651 1.471376 0.895443 H 1.937332 0.100582 1.209557 H 4.929367 0.640189 1.014053 H 0.433306 1.754237 0.899393 C 4.762916 1.347076 1.449089 H 4.337995 2.331552 1.680137 H 5.773270 1.504159 1.055568 H 4.868080 0.795626 2.388894 C 2.202809 0.096824 2.271623 H 1.139099 0.237227 2.495582 H 2.586723 0.641310 2.983569 H 2.709786 1.046797 2.479641 C 7.541314 1.333143 0.430199 H 8.007376 2.230697 0.859433 O 8.573914 0.450669 0.062606 C 9.551495 0.029730 0.755050 O 10.402903 0.742444 0.281186 C 9.508436 0.355290 2.222853 H 9.570581 1.441182 2.355513 H 8.57 9059 0.019489 2.696694 H 10.355563 0.116268 2.721244 H 4.925493 1.815407 1.828118 H 6.967110 0.837063 1.217942 C 0.139164 1.768699 1.121642 C 2.573582 0.404401 1.347436 H 0.912398 2.512977 0. 968621 H 0.104585 1.509983 2.148248 H 2.956790 1.422656 1.213596 C 3.174905 0.291811 2.528144 H 4.062562 0.848762 2.176534 H 2.476837 1.012797 2.959429

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142 O 3.594316 0.714192 3.471893 C 3.767372 0.434675 4.797884 O 4.124011 1.330195 5.525272 C 3.501312 0.980497 5.270106 H 4.115357 1.706398 4.725226 H 2.455157 1.267296 5.116793 H 3.739795 1.029905 6.332895 TS20 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1487556400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2674331000 a.u Ru 1.324831 0.397306 0.317466 O 0.869272 1.817880 3.281821 O 0.233794 1.118526 1.503260 N 2.692275 1.043450 2.1253 03 N 2.754192 1.147303 2.079720 C 2.343863 0.040422 1.404287 C 3.207999 0.707555 3.457013 C 2.316517 2.372236 1.621406 C 0.915173 2.778468 2.143706 C 0.497511 4.132801 1.536721 C 1.532585 5 .206909 1.927392 C 2.920715 4.800160 1.392078 C 3.335433 3.455861 2.033809 C 2.856417 4.658497 0.144050 C 1.825574 3.566264 0.534101 C 2.302586 2.225443 0.070100 C 0.441097 3.993561 0.002904 C 2.748733 2.498258 1.596903 C 1.779982 3.390761 2.103777 C 1.770760 4.704264 1.630579 C 0.794215 2.964850 3.167668 C 3.536091 0.786236 3.283051 C 3.732577 2.935882 0.690543 C 2.699994 5.156872 0.685044 C 3.674911 4.262217 0.240296 C 4.873887 2.057891 0.226135 C 2.639939 6.571540 0.158004 H 3.355339 2.093651 0.220784 H 4.085615 1.306182 3.711754 H 2.439957 0.875794 4.224696 H 0.183600 2.002059 1.871544 H 0.926032 2.835690 3.242219 H 0.490824 4.412419 1.924477 H 1.566988 5.327919 3.019647 H 1.239022 6.177900 1.507335 H 3.660232 5.564482 1.664364 H 4.340180 3.162 684 1.700491 H 3.370589 3.567904 3.128149 H 3.848089 4.402740 0.542315 H 2.572923 5.621774 0.590798 H 1.786449 3.480572 1.624842 H 0.326028 3.267133 0.282842 H 0.152030 4.952827 0.447069 H 1.019349 5.393564 2.010311 H 0.410293 1.955703 2.994468 H 0.054636 3.654077 3.211185 H 1.259317 2.964566 4.163233 H 3.237190 1.394592 4.140428 H 4.605411 0.953966 3.096865 H 4.423504 4.601339 0.472867 H 5.821588 2.414705 0.650546 H 4.980886 2.082512 0.863359 H 4.746996 1.014984 0.523168 H 1.884599 6.665504 0.633193 H 3.599326 6.881402 0.268055 H 2.371526 7.282516 0.947249 C 6.965 776 1.753733 0.907827 H 7.500503 2.163172 1.763405 N 0.183669 1.816931 2.623516 O 1.210412 2.400387 2.957044 C 2.662565 0.230802 0.728571 C 2.227714 0.897887 0.246395 C 4.696130 1.010046 0.0 24342 C 4.144617 0.434656 0.313402 H 2.099023 1.143333 0.501473 H 4.105867 0.965001 0.647237 C 3.420598 1.890379 0.189463 H 3.310414 2.562713 0.671873 H 3.460339 2.528546 1.078169 C 0.915108 1.586213 0.000472 C 5.641382 1.577980 1.000960 H 2.193460 0.455071 1.247668 H 5.212939 0.945935 0.986659 H 0.716939 1.911914 1.020013 C 5.011865 1.276376 1.252100 H 4.584828 2.279604 1.371629 H 6.025323 1.389263 0.851361 H 5.111087 0.830880 2.247157 C 2.459320 0.097299 2.215958 H 1.395252 0.211244 2.454285 H 2.844837 0.709512 2.847902 H 2.965104 1.021610 2.520802 C 7.838771 1.4 10252 0.261802 H 8.451183 2.276560 0.545085 O 8.705109 0.329172 0.154062 C 9.670739 0.167090 0.668554 O 10.382142 1.051475 0.257217 C 9.791853 0.418748 2.063841 H 10.020923 1.489841 2.031253 H 8.861376 0.299247 2.630192 H 10.596650 0.103907 2.581130 H 5.175116 1.877051 1.941433 H 7.254046 1.105423 1.134552 C 0.042677 1.950637 0.959279 C 2.562055 0.334045 1.434875 H 0.812120 2.578103 0.728246 H 0.217128 1.705906 2.003886

PAGE 150

143 H 2.569893 1.425353 1.588801 C 3.584585 0.364160 2.289145 H 4.308322 0.897510 1.663135 H 3.091422 1.104725 2.925413 O 4.368076 0.582507 3.039653 C 4.0 29661 0.980681 4.304249 O 4.627631 1.915790 4.780210 C 2.964435 0.198440 5.044808 H 3.289433 0.835425 5.211243 H 2.017165 0.143944 4.500240 H 2.809021 0.681052 6.010105 16 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1647.0138355800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1646.4017609600 a.u Ru 0.335776 0.300604 0.695863 O 1.350872 3.301261 1.030158 O 1.093829 1.461277 2.229054 N 0.948046 2.109178 0.752420 N 1.210557 2.218559 0.371778 C 0.102866 1.460862 0.217407 C 0.624230 3.483119 1.154619 C 2.269787 1.482231 0.618762 C 2.966280 1.937537 0.689406 C 4.299397 1.183786 0.867495 C 5.2123 95 1.475412 0.340679 C 4.516722 1.008030 1.635915 C 3.195008 1.791524 1.814272 C 4.228600 0.506379 1.543471 C 3.300525 0.797707 0.333167 C 1.976846 0.046889 0.573821 C 4.010550 0.327922 0.95 5218 C 2.544429 1.835593 0.006074 C 3.014958 2.186179 1.276787 C 4.316942 1.827917 1.626978 C 2.131397 2.919136 2.259346 C 0.921657 3.453941 1.133123 C 3.361312 1.148997 0.920393 C 5.156928 1.135906 0.743289 C 4.662031 0.811340 0.520075 C 2.892786 0.751248 2.302344 C 6.552232 0.735110 1.162281 H 1.608428 0.322747 1.572982 H 1.027258 3.716137 2.143544 H 1.033617 4.206348 0.436393 H 2.303035 1.739923 1.545427 H 3.138667 3.023467 0.662574 H 4.785033 1.525585 1.790530 H 5.440021 2.549486 0.398049 H 6.170177 0.952323 0.220168 H 5.165743 1.209754 2.497890 H 2.697846 1.50 2152 2.749764 H 3.409410 2.869095 1.874179 H 3.760918 0.860043 2.472674 H 5.173109 1.056668 1.432783 H 3.101889 1.873182 0.276728 H 3.394771 0.545564 1.834153 H 4.951386 0.880364 1.080136 H 4.686889 2.093533 2.615103 H 1.255198 2.318886 2.532784 H 2.681015 3.148044 3.177020 H 1.756809 3.865286 1.849575 H 1.358528 4.325412 0.637813 H 1.347175 3.384290 2.142379 H 5.298672 0.273696 1.219771 H 3.531661 1.197867 3.074210 H 2.942767 0.336326 2.430962 H 1.862730 1.058855 2.495513 H 6.529625 0.150973 1.809940 H 7.176499 0.492574 0.296771 H 7.046344 1.534415 1.726090 N 1.57 7479 2.695447 2.089907 O 2.198809 3.154505 3.037514 C 0.797890 1.313368 0.272717 H 1.822701 1.406340 0.139484 C 0.541784 2.169168 1.481528 H 0.126054 1.571699 2.299279 H 0.196548 2.937129 1. 226021 O 1.754097 2.733655 2.008831 C 2.270384 3.912855 1.537713 O 3.372183 4.234163 1.910805 C 1.411060 4.757303 0.618550 H 0.520903 5.118791 1.147243 H 1.055254 4.210746 0.260069 H 2.005879 5.614801 0.302965 TS24 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1647.0131889300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1646.3993179400 a.u Ru 0.293924 0.334134 0.563443 O 1.255898 3.152145 1.184764 O 0.909671 1.298451 2.321395 N 0.975120 2.125727 0.725098 N 1.184560 2.255220 0.333995 C 0.093296 1.462258 0.236910 C 0.682858 3.537583 0.994672 C 2.285915 1.474911 0.594628 C 2.954795 1.853851 0.75168 4 C 4.270669 1.070036 0.926825 C 5.220139 1.404195 0.241129 C 4.551503 1.013388 1.575406 C 3.246743 1.827511 1.748945 C 4.241167 0.499995 1.564510 C 3.275038 0.835095 0.395680 C 1.972320 0. 051134 0.640936 C 3.952290 0.438280 0.933898 C 2.521578 1.875814 0.021767 C 2.931210 2.005499 1.362274

PAGE 151

144 C 4.239028 1.637380 1.693436 C 1.990401 2.520529 2.426795 C 0.862711 3.533029 1.005961 C 3.400893 1.400178 0.969328 C 5.136517 1.151487 0.736748 C 4.698847 1.045555 0.587279 C 2.976057 1.267961 2.413860 C 6.532947 0.726571 1.127019 H 1.632082 0.266494 1.664544 H 1.109785 3.86122 4 1.947268 H 1.086397 4.178390 0.198492 H 2.267873 1.627360 1.580453 H 3.146931 2.936301 0.780445 H 4.736251 1.357206 1.878292 H 5.466519 2.475594 0.239013 H 6.165877 0.859168 0.122580 H 5.226094 1.246278 2.409358 H 2.769877 1.594171 2.710220 H 3.479937 2.902838 1.749079 H 3.795922 0.802709 2.522251 H 5.175437 1.067471 1.453824 H 3.060016 1.909308 0.391293 H 3.304665 0.678152 1.783660 H 4.877545 1.015533 1.062572 H 4.564270 1.734437 2.726942 H 1.171614 1.814462 2.612780 H 2.521208 2.672243 3.371116 H 1.531676 3.474425 2.140260 H 1.297143 4.375450 0.460906 H 1.261 911 3.538920 2.027622 H 5.382025 0.668530 1.345326 H 3.037925 2.228551 2.943467 H 3.623582 0.563942 2.944200 H 1.945729 0.909523 2.502720 H 6.570253 0.349025 1.343846 H 7.250764 0.919710 0.3 22754 H 6.875792 1.252514 2.024016 N 1.363614 2.546076 2.266491 O 1.845558 3.016967 3.284926 C 0.815751 1.250725 0.536652 H 1.906060 1.155503 0.382185 C 0.428836 2.258915 1.586004 H 0.051576 1.749419 2.431029 H 0.295440 2.973905 1.183130 O 1.576180 2.912249 2.152068 C 2.109339 4.046884 1.602046 O 3.153914 4.453814 2.049881 C 1.339173 4.743726 0.498301 H 0.388781 5.137263 0.878232 H 1.093001 4.081790 0.337323 H 1.947791 5.575738 0.143301 TS21 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1582103400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2691925100 a.u Ru 1.269241 0.473264 0.274876 O 0.076840 1.818967 1.163859 O 0.325585 1.829546 0.965809 N 3.881794 0.427066 0.980102 N 3.211638 1.651603 1.084977 C 2.851239 0.399437 0.654697 C 4.895261 0.200628 1.831910 C 3.736457 1.8 78576 0.835034 C 3.274303 2.525267 2.166646 C 3.076013 4.043431 1.975823 C 4.395640 4.687394 1.509151 C 4.826490 4.049822 0.172466 C 5.066763 2.539973 0.398480 C 3.718272 4.267797 0.882769 C 2.397521 3.597162 0.411739 C 2.690294 2.081744 0.277105 C 1.983794 4.275347 0.914882 C 2.511833 2.897101 0.976619 C 1.690677 3.303597 2.051792 C 1.051384 4.542238 1.973156 C 1.530460 2.443427 3.285706 C 4.582045 1.685949 1.636760 C 2.743895 3.754692 0.114464 C 1.220236 5.395887 0.874368 C 2.077323 4.988033 0.148353 C 3.711962 3.414711 1.226001 C 0.489471 6.716365 0.804556 H 3.1 91289 1.797739 1.214034 H 5.906864 0.063595 1.513753 H 4.771589 0.112061 2.877899 H 2.336091 2.059831 2.489253 H 4.024553 2.344851 2.950356 H 2.765357 4.487073 2.930934 H 5.181874 4.547321 2 .265126 H 4.260975 5.770338 1.384992 H 5.761003 4.510984 0.174035 H 5.426774 2.060375 0.521863 H 5.846955 2.409096 1.163421 H 4.031932 3.852212 1.850581 H 3.562537 5.345507 1.033689 H 1.620683 3.760984 1.168165 H 1.029292 3.897101 1.282428 H 1.857731 5.353779 0.743677 H 0.410080 4.854833 2.794641 H 1.270974 1.408199 3.043046 H 0.750999 2.846682 3.938958 H 2.460382 2.407779 3.8686 47 H 4.611057 2.260822 2.566640 H 5.264481 2.162204 0.919755 H 2.242121 5.646235 0.999070 H 4.632896 4.004978 1.129641 H 3.284017 3.650937 2.206519 H 3.992217 2.359478 1.223610

PAGE 152

145 H 0.569085 6 .568428 0.554854 H 0.919144 7.372680 0.041435 H 0.523299 7.243542 1.764794 C 6.434627 0.211615 1.090076 H 7.097383 0.786260 1.734877 N 0.609942 2.310076 0.197391 O 1.468380 3.159703 0.358711 C 2.647949 1.548582 1.489991 C 1.810372 0.536107 0.641657 C 4.174633 0.134128 0.109027 C 4.030158 0.840894 1.522402 H 2.240165 1.602139 2.509216 H 3.929907 0.023799 2.249225 C 2.758092 0.2151 88 0.530106 H 2.735171 1.026944 1.268777 H 2.492176 0.702841 1.057624 C 0.404963 1.029163 0.344681 C 5.234044 0.720732 0.783895 H 1.731167 0.357216 1.271553 H 4.411336 0.917203 0.297613 H 0.068669 1.479105 1.210957 C 5.221896 1.690423 1.971237 H 5.058325 2.076750 2.984958 H 6.141710 1.095861 1.981141 H 5.397951 2.545622 1.311057 C 2.677733 2.974820 0.921823 H 1.669953 3.401648 0.876892 H 3.286581 3.631250 1.552698 H 3.097589 3.013328 0.090025 C 7.004554 1.082033 0.589430 H 7.490564 1.625270 1.409326 O 7.990222 0.761075 0.423573 C 8.745058 1.728418 1.013537 O 9.547 026 1.403456 1.856080 C 8.534246 3.166797 0.576082 H 8.766361 3.298259 0.486871 H 7.497076 3.486364 0.726613 H 9.195839 3.800230 1.167350 H 4.985005 1.688159 1.224016 H 6.233097 1.728469 0.1 60914 C 0.016319 1.521639 0.904075 C 1.593544 0.405261 1.912867 H 0.674179 2.381545 0.931071 H 0.640196 1.414087 1.762400 H 2.253199 1.259452 2.096509 C 1.035051 0.119342 3.206066 H 1.833236 0.714471 3.679641 H 0.169759 0.768661 3.049991 O 0.692030 0.995993 4.059446 C 0.179691 0.813451 5.311009 O 0.098371 1.788034 5.966599 C 0.008123 0.610057 5.799601 H 0.937994 1.162565 5.798110 H 0.708697 1.160913 5.162102 H 0.401117 0.570774 6.815697 TS22 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1462027800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2647094000 a.u Ru 0.991170 0.633373 0.443729 O 0.589630 0.946596 3.267759 O 0.417296 0.916498 2.084085 N 2.263375 2.269425 1.575980 N 2.896441 0.235192 2.085708 C 2.166671 0.971682 1.187532 C 2.885077 2.442366 2.890966 C 1.426017 3.2 69712 0.907383 C 0.054874 3.396595 1.622075 C 0.858391 4.364229 0.845905 C 0.183179 5.749550 0.773372 C 1.178236 5.621911 0.059194 C 2.089043 4.664258 0.865310 C 0.949870 5.073651 1.366448 C 0.284524 3.675181 1.295092 C 1.243790 2.739410 0.531343 C 1.072911 3.807460 0.575213 C 3.323302 1.132595 1.973863 C 2.700862 2.116969 2.766566 C 3.123082 3.446058 2.636697 C 1.640760 1.784144 3.793869 C 3.594372 1.095169 3.066712 C 4.432522 1.461586 1.162509 C 4.158337 3.815128 1.775344 C 4.812451 2.802822 1.064000 C 5.266630 0.410634 0.459118 C 4.565932 5.260447 1.612861 H 2.2 30446 2.806808 1.018841 H 3.573948 3.290794 2.903276 H 2.120634 2.608226 3.663322 H 0.412640 2.403081 1.684946 H 0.199103 3.752342 2.652700 H 1.821443 4.449249 1.366789 H 0.046912 6.160039 1 .784246 H 0.827282 6.452108 0.228028 H 1.660443 6.606846 0.006577 H 3.078769 4.585837 0.395631 H 2.236440 5.067245 1.878780 H 1.905425 5.010030 1.905366 H 0.312444 5.770173 1.929606 H 0.119754 3.288459 2.304360 H 1.569934 2.830769 0.535607 H 1.733586 4.476158 1.143697 H 2.628976 4.210981 3.232509 H 1.223593 0.784805 3.651875 H 0.818287 2.506798 3.764341 H 2.064978 1.825990 4.8060 96 H 3.501150 0.683936 4.075667 H 4.661907 1.156747 2.817864

PAGE 153

146 H 5.647222 3.062071 0.416242 H 6.122110 0.121931 1.085118 H 5.674152 0.800779 0.478924 H 4.704577 0.498136 0.231916 H 4.184287 5 .672064 0.669686 H 5.656062 5.369494 1.592908 H 4.176472 5.881050 2.426021 C 5.772183 2.382172 1.038436 H 6.150739 3.275024 1.531107 N 1.037607 0.184628 2.975565 O 2.044601 0.660198 3.494710 C 2.063797 1.872792 1.836524 C 1.465760 0.874221 0.789921 C 3.838527 1.281201 0.197284 C 3.576736 1.553169 1.730047 H 1.705228 1.615316 2.843246 H 3.707913 0.580447 2.224981 C 2.431075 0.9826 43 0.407147 H 2.127574 1.794993 1.076048 H 2.450188 0.072176 1.005998 C 0.032554 1.084683 0.587222 C 4.531659 2.398135 0.534717 H 1.600699 0.124191 1.238237 H 4.465891 0.387129 0.129170 H 0.538997 1.188600 1.541193 C 4.538533 2.528636 2.412194 H 4.307644 2.613396 3.481545 H 5.570247 2.176504 2.313642 H 4.493141 3.532836 1.978024 C 1.697823 3.339854 1.570751 H 0.616809 3.498137 1.652068 H 2.183852 3.998774 2.297865 H 1.997933 3.672676 0.570812 C 6.718630 1.215506 0.957787 H 7.551312 1.354351 1.655079 O 7.227118 1.123621 0.398231 C 8.159398 0.197830 0.750688 O 8.49 2603 0.126177 1.910007 C 8.737204 0.686881 0.339120 H 9.263564 0.091196 1.093781 H 7.955921 1.253808 0.857352 H 9.440258 1.379753 0.123669 H 3.951343 3.312510 0.665389 H 6.213411 0.277074 1. 213785 C 0.661047 1.738824 0.491041 C 2.302045 0.329647 1.345757 H 1.536555 2.348450 0.289344 H 0.131736 1.943764 1.414883 H 3.141027 0.811537 0.842690 C 2.415738 0.435057 2.839210 H 2.979525 0.441283 3.200411 H 1.435474 0.454095 3.311647 O 3.170820 1.629359 3.131949 C 3.115386 2.236002 4.354476 O 3.780709 3.229147 4.526423 C 2.221413 1.624726 5.414608 H 2.480959 0.576487 5.60179 5 H 1.169001 1.651852 5.110474 H 2.349457 2.198065 6.333141 TS25 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1639615600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2771874200 a.u Ru 0.780198 0.619126 0.61956 4 O 1.331177 0.963157 2.900066 O 0.694124 0.477942 2.283995 N 2.132870 2.558915 1.057361 N 3.186269 0.694238 1.507960 C 2.212429 1.246756 0.714345 C 2.929110 2.919703 2.232048 C 1.054636 3. 393853 0.522557 C 0.144939 3.447797 1.501134 C 1.306317 4.231021 0.859451 C 0.839661 5.671285 0.565726 C 0.362982 5.632924 0.399984 C 1.522610 4.846135 0.255663 C 0.069534 4.948719 1.714014 C 0.523901 3.494045 1.424818 C 0.676032 2.737366 0.818358 C 1.720828 3.535405 0.453453 C 3.928298 0.518849 1.305339 C 3.771687 1.578421 2.220010 C 4.560487 2.720432 2.057434 C 2.795289 1.49675 2 3.370855 C 3.851476 1.705769 2.362661 C 4.907663 0.573538 0.294029 C 5.510100 2.825395 1.037557 C 5.682417 1.733428 0.182301 C 5.110313 0.567596 0.677160 C 6.290107 4.102168 0.840548 H 1. 534189 2.896183 1.488015 H 3.475130 3.854398 2.077182 H 2.283613 3.043823 3.112202 H 0.456663 2.427040 1.745138 H 0.156948 3.932358 2.441036 H 2.155784 4.253915 1.555728 H 0.562221 6.177463 1.501560 H 1.659492 6.250823 0.120135 H 0.702164 6.656415 0.607495 H 2.400099 4.832138 0.404059 H 1.819460 5.345700 1.190253 H 0.759727 4.944840 2.433705 H 0.888867 5.519494 2.174211 H 0.837093 3.025812 2.362651 H 2.073909 2.517463 0.250742 H 2.558267 4.078484 0.913710 H 4.422524 3.554205 2.742033 H 1.809569 1.146260 3.050215

PAGE 154

147 H 2.673066 2.476025 3.843121 H 3.142090 0.801071 4.146723 H 3.944914 1.341143 3.389208 H 4.860491 1.908949 1.982648 H 6.429055 1.788568 0.607234 H 5.358445 1.506967 0.168358 H 5.927798 0.341905 1.368171 H 4.208645 0.757200 1.270352 H 5.680 567 4.831219 0.291342 H 7.206962 3.931898 0.266709 H 6.565000 4.560268 1.797128 C 5.633093 2.746639 0.638952 H 5.835563 3.779890 0.914318 N 0.114216 0.774353 3.249085 O 0.268808 0.866465 4.4 02063 C 2.265371 1.051860 2.209678 C 1.730582 0.228162 0.998508 C 3.955118 1.106495 0.375167 C 3.793903 1.006980 1.947025 H 2.040860 0.516811 3.143531 H 4.107226 0.014507 2.205047 C 2.552875 0.744127 0.202755 H 2.083599 1.636565 0.635085 H 2.610431 0.016024 1.012805 C 0.228728 0.027145 0.876417 C 4.437698 2.444345 0.115403 H 2.080273 0.801250 1.191340 H 4.680166 0.343111 0.075996 H 0.234080 0.106632 1.870726 C 4.666666 1.958073 2.768725 H 4.544017 1.763168 3.841299 H 5.724603 1.825174 2.518627 H 4.423688 3.010284 2.588945 C 1.684449 2.466641 2.343440 H 0.599706 2.4 36899 2.493585 H 2.116354 2.980742 3.208449 H 1.881588 3.091886 1.464614 C 6.767619 1.786810 0.851082 H 7.343903 2.076000 1.737112 O 7.621551 1.831396 0.320129 C 8.802088 1.154228 0.365780 O 9.451879 1.192711 1.383062 C 9.238772 0.391990 0.872453 H 9.403817 1.070157 1.717505 H 8.487148 0.341776 1.183645 H 10.171923 0.122088 0.641158 H 3.721419 3.262079 0.019167 H 6.407700 0.763375 0.998141 C 0.755127 1.654993 0.000872 C 1.178020 1.411982 1.342153 C 2.558884 1.750181 1.840922 H 3.284492 1.826464 1.036625 H 2.885288 1.035901 2.596806 O 2.523655 3.018050 2.565343 C 2.644842 4.151333 1.843786 O 2.796538 4.187375 0.639462 C 2.566575 5.365357 2.743652 H 3.315801 5.298371 3.538921 H 1.584426 5.408389 3.226553 H 2.726243 6.268203 2.152721 H 0.189785 2.171130 0.128410 H 1.511287 1.899794 0.735779 H 0.420100 1.566205 2.109863 TS26 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.161515950 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2838450500 a.u Ru 1.007323 0.771981 0.572936 O 1.043344 2.402280 3.481546 O 0.721794 0.936844 1.891472 N 3.001037 1.986727 1.132034 N 3.315973 0.146633 1.492979 C 2.588144 0.746010 0.746966 C 3.898607 1.987606 2.290272 C 2.225 899 3.161101 0.734129 C 1.153762 3.506383 1.805917 C 0.294301 4.694412 1.332736 C 1.203588 5.917448 1.095855 C 2.260273 5.574817 0.024694 C 3.128701 4.398451 0.519938 C 1.550446 5.177058 1.283781 C 0.636274 3.944657 1.045404 C 1.526655 2.779473 0.580362 C 0.416415 4.302385 0.024577 C 3.412188 1.575130 1.383333 C 2.652261 2.391354 2.243207 C 2.755993 3.781964 2.105555 C 1.80492 2 1.826772 3.362292 C 4.313440 0.516756 2.359912 C 4.376875 2.143744 0.522214 C 3.622284 4.373014 1.184446 C 4.450942 3.534755 0.430865 C 5.354967 1.295498 0.262407 C 3.657583 5.868094 0.983 567 H 2.301088 2.589484 1.356037 H 4.746466 2.661428 2.140211 H 3.363646 2.308482 3.194088 H 0.521680 2.623400 1.976046 H 1.640834 3.750666 2.760408 H 0.447731 4.930383 2.106888 H 1.695760 6.214898 2.033092 H 0.600419 6.773703 0.766476 H 2.906083 6.445285 0.149872 H 3.910185 4.158273 0.213452 H 3.631539 4.678726 1.457159 H 2.289645 4.951572 2.064717 H 0.944800 6.015939 1.652848 H 0.149979 3.697306 1.989514

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148 H 1.090855 3.454930 0.188519 H 1.039096 5.133049 0.332280 H 2.144897 4.416945 2.743770 H 1.591544 0.764228 3.230008 H 0.853184 2.359837 3.451444 H 2.326338 1.943 304 4.322306 H 4.274869 0.102329 3.371541 H 5.323356 0.353799 1.964346 H 5.164697 3.976904 0.260794 H 6.260960 1.101112 0.327645 H 5.674168 1.810506 1.173705 H 4.935117 0.327703 0.548479 H 3.131912 6.134685 0.057814 H 4.684989 6.239042 0.893859 H 3.173529 6.398925 1.809416 C 6.049081 1.966260 0.511040 H 6.509931 2.857127 0.935201 N 1.395038 1.946994 2.388245 O 2.375391 2.362305 1.755084 C 1.945919 1.550054 1.916522 C 1.524096 0.549186 0.795135 C 3.945603 0.962387 0.558527 C 3.463378 1.257490 2.034385 H 1.446440 1.289337 2.860941 H 3.539703 0.299023 2.566705 C 2.636865 0.720410 0.259632 H 2.435919 1.589596 0.898204 H 2.717743 0.147241 0.910949 C 0.035448 0.637601 0.426752 C 4.792248 2.044391 0.055519 H 1.658778 0.452934 1.231508 H 4.520388 0.031649 0.579645 H 0.518057 0.953010 1.309164 C 4.296357 2.268459 2.827050 H 3.914954 2.365234 3.851431 H 5.341882 1.946569 2.889145 H 4.293264 3.265063 2.374507 C 1.609023 3.015115 1.597351 H 0.530 263 3.157281 1.468143 H 1.932406 3.676599 2.408544 H 2.093925 3.363957 0.678831 C 6.935251 0.757693 0.518284 H 7.201023 0.489894 1.549762 O 8.136300 1.103720 0.209771 C 9.182421 0.240264 0.3 07203 O 10.161272 0.582753 0.927127 C 9.059466 1.112094 0.371458 H 8.938532 1.005041 1.455339 H 8.194014 1.672615 0.000976 H 9.969330 1.676884 0.167243 H 4.299164 3.012578 0.155794 H 6.453712 0.108994 0.056641 C 0.455823 1.468784 0.832572 C 1.359120 0.687366 1.883982 C 2.680448 1.298379 2.280942 H 3.122103 1.899959 1.491475 H 3.378130 0.523043 2.605561 O 2.516031 2.131919 3.465907 C 2.263243 3.445577 3.276222 O 2.186105 3.978978 2.188062 C 2.086111 4.149641 4.602236 H 2.927911 3.933468 5.267110 H 1.179438 3.781876 5.095139 H 2.001169 5.224269 4.436307 H 0.435548 1.7 84468 1.375001 H 1.036908 2.320447 0.478123 H 0.783227 0.434583 2.777190 TS27 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1661749300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2759858400 a.u Ru 1.089974 0.6 30889 0.356606 O 0.138431 1.815604 1.360810 O 0.601243 2.009673 0.668955 N 3.889899 0.564632 0.398384 N 3.207329 1.502867 0.691370 C 2.803414 0.249352 0.291981 C 5.066034 0.071227 0.997565 C 3.712005 2.022957 0.371061 C 3.511498 2.571033 1.809663 C 3.263689 4.093152 1.767104 C 4.461027 4.797020 1.100141 C 4.632651 4.257095 0.334071 C 4.925815 2.740245 0.265751 C 3.338291 4.519640 1.137505 C 2.140327 3.789711 0.467652 C 2.466426 2.277676 0.490817 C 1.981553 4.364152 0.957582 C 2.401029 2.609420 1.128781 C 1.774149 2.530744 2.395881 C 1.058634 3.636464 2.857174 C 1.8 72293 1.286435 3.249562 C 4.635514 1.542258 1.081487 C 2.368733 3.802473 0.386438 C 0.965621 4.822444 2.115629 C 1.636415 4.885907 0.895018 C 3.096361 3.973071 0.927827 C 0.161912 5.993257 2 .631189 H 2.771704 2.063004 1.526056 H 5.951607 0.069775 0.370168 H 5.281962 0.356401 1.984740 H 2.656868 2.066530 2.274097 H 4.400010 2.359028 2.421855 H 3.140685 4.464319 2.793203 H 5.379440 4.628019 1.680972 H 4.292935 5.882132 1.076392 H 5.478084 4.761078 0.821292 H 5.103750 2.334109 1.270916

PAGE 156

149 H 5.840982 2.572458 0.322143 H 3.460056 4.176488 2.174222 H 3.146579 5.601373 1.179928 H 1.230922 3.981097 1.048808 H 1.123587 3.927376 1.471468 H 1.803194 5.446981 0.895046 H 0.569051 3.575763 3.826952 H 1.375560 0.427923 2.783473 H 1.407630 1.454151 4.225675 H 2.91492 5 0.994004 3.424492 H 4.740385 1.961258 2.087354 H 5.199759 2.182704 0.393321 H 1.602270 5.806775 0.316337 H 3.634525 4.927854 0.944715 H 2.397199 3.978131 1.771864 H 3.820951 3.174796 1.103 546 H 0.914437 5.817103 2.507085 H 0.408260 6.915433 2.095568 H 0.339822 6.162469 3.699341 C 6.441298 0.283526 1.162208 H 7.079160 0.858833 1.831570 N 0.698851 2.377133 0.561903 O 1.521103 3.194696 0.936766 C 2.612387 1.646476 1.429381 C 1.857865 0.538778 0.624291 C 4.259682 0.238837 0.184099 C 4.031615 1.025309 1.539918 H 2.172426 1.739380 2.432053 H 3.958524 0.253264 2.317605 C 2.857629 0.195207 0.496148 H 2.815646 0.953425 1.289011 H 2.656339 0.770532 0.963831 C 0.432755 0.921947 0.261067 C 5.299581 0.831670 0.727432 H 1.810424 0.318087 1.308036 H 4.551401 0.783 161 0.443114 H 0.075957 1.424472 1.076373 C 5.156749 1.972895 1.965771 H 4.930607 2.424975 2.939511 H 6.105287 1.432866 2.061022 H 5.318334 2.785982 1.250848 C 2.574243 3.034744 0.773867 H 1.545381 3.399434 0.685745 H 3.132132 3.762479 1.373477 H 3.012378 3.036908 0.231099 C 6.973639 1.079456 0.835705 H 7.020295 1.696354 1.743993 O 8.310018 0.900333 0.316073 C 9.083362 1.961321 0.040847 O 10.201149 1.752325 0.448030 C 8.491145 3.353239 0.087810 H 8.209298 3.576131 1.122974 H 7.590734 3.463720 0.526941 H 9.241497 4.071804 0.242482 H 5.072495 1.835645 1.090034 H 6.350 379 1.600355 0.103320 C 0.029674 1.345800 1.041141 C 1.144265 0.043148 2.124268 C 2.186680 0.787678 2.901279 H 2.558531 1.670956 2.383277 H 3.022836 0.095014 3.062976 O 1.770305 1.140275 4.248692 C 1.189783 2.344638 4.433939 O 1.009877 3.159672 3.551020 C 0.798123 2.535321 5.880587 H 1.669060 2.399702 6.529732 H 0.057442 1.781627 6.168541 H 0.380862 3.533584 6.016547 H 0.78036 6 1.317747 1.826648 H 0.665213 2.172200 1.117124 H 0.392936 0.407620 2.790837 TS28 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1517774700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2690445400 a.u Ru 1.08355 8 0.680208 0.466292 O 0.067828 2.347749 3.195956 O 0.730761 1.390006 1.370281 N 3.444871 1.351216 1.079839 N 3.427788 0.844049 1.148985 C 2.755744 0.253445 0.661342 C 4.517244 1.053816 2.033 186 C 2.777616 2.659076 1.001320 C 1.857795 2.861353 2.237377 C 1.069441 4.178211 2.104947 C 2.067622 5.350477 2.007445 C 2.977634 5.152179 0.777388 C 3.775048 3.834711 0.932287 C 2.101754 5.094946 0.491790 C 1.107782 3.908189 0.399040 C 1.926506 2.606974 0.280320 C 0.202353 4.114206 0.831503 C 2.923647 2.175407 1.354185 C 2.031956 2.396933 2.432557 C 1.569774 3.692203 2.667602 C 1.622670 1.276561 3.363005 C 4.667088 0.463459 1.868310 C 3.421052 3.260162 0.611972 C 1.984074 4.780432 1.887040 C 2.920823 4.542942 0.883504 C 4.509749 3.126202 0.428442 C 1.436170 6.165 205 2.139114 H 2.627421 2.583637 1.129105 H 5.433334 1.596048 1.784367 H 4.220336 1.334544 3.053356 H 1.161548 2.012564 2.306897 H 2.453113 2.868278 3.161920 H 0.431932 4.308116 2.989786

PAGE 157

150 H 2.671851 5.411089 2.924159 H 1.523649 6.300394 1.920519 H 3.686059 5.987904 0.705308 H 4.452367 3.693119 0.079374 H 4.394538 3.884664 1.840690 H 2.731207 4.985405 1.385158 H 1.552858 6.040860 0.603418 H 0.508062 3.878157 1.311102 H 0.524583 3.294229 0.904849 H 0.375841 5.042238 0.725142 H 0.879410 3.860814 3.491411 H 1.151817 0.441661 2.834973 H 0.916118 1.640473 4.114595 H 2.488 235 0.864555 3.898029 H 4.736300 0.996869 2.820247 H 5.546688 0.727160 1.267620 H 3.291220 5.378144 0.292644 H 5.362995 3.763441 0.165169 H 4.149525 3.451056 1.410325 H 4.875294 2.101140 0.5 17430 H 0.426168 6.270680 1.722200 H 2.063675 6.934559 1.678422 H 1.366008 6.379801 3.211524 C 6.365522 1.587868 0.981425 H 6.935107 2.453719 1.314765 N 0.912528 2.050737 2.492008 O 2.077093 2.329153 2.784943 C 2.391416 1.366509 1.606609 C 1.722516 0.630966 0.406506 C 4.135319 0.735916 0.060312 C 3.849923 0.847358 1.495461 H 1.950239 1.021366 2.553331 H 3.825358 0.188054 1.862261 C 2.735733 0.829438 0.738070 H 2.604273 1.820694 1.192484 H 2.614527 0.083190 1.524349 C 0.273495 1.040158 0.166107 C 5.095633 1.764252 0.592873 H 1.744531 0.438051 0.660991 H 4.547722 0.2 60769 0.242250 H 0.233035 1.397817 1.056678 C 4.908414 1.584183 2.319353 H 4.660617 1.547204 3.387664 H 5.893452 1.124509 2.184738 H 5.004316 2.636611 2.033563 C 2.260670 2.896486 1.559758 H 1.210168 3.206668 1.586835 H 2.761912 3.355044 2.418969 H 2.705476 3.324817 0.654433 C 7.123931 0.294209 0.965090 H 7.744760 0.208203 1.864819 O 7.975896 0.296050 0.209077 C 8.869337 0.704212 0.440420 O 9.538351 0.662306 1.445497 C 8.976886 1.818931 0.584535 H 9.303611 1.434039 1.557314 H 8.015382 2.321062 0.738373 H 9.708246 2.541842 0.222490 H 4.699395 2.779262 0.657217 H 6.4 53173 0.569160 0.929136 C 0.248283 1.532273 1.039500 C 1.645720 0.022398 2.085729 C 2.952015 0.624667 2.493933 H 3.278028 1.414603 1.822738 H 3.705883 0.172153 2.503613 O 2.930541 1.112284 3.858538 C 2.558860 2.397674 4.047886 O 2.291522 3.167278 3.146189 C 2.518223 2.733716 5.519336 H 3.451621 2.435935 6.006423 H 1.707472 2.175109 6.000042 H 2.348845 3.803706 5.644649 H 0.37365 5 1.534265 1.929667 H 1.064435 2.245134 1.032973 H 0.998455 0.229669 2.932741 TS29 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1403671500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2647094000 a.u Ru 0.90714 3 0.441837 0.462170 O 1.060644 0.015844 3.362500 O 0.466922 1.483749 1.818124 N 2.762195 1.199155 1.625421 N 3.174743 0.934330 1.412397 C 2.389877 0.091958 0.940076 C 3.890691 1.009247 2.537 877 C 1.980739 2.432357 1.552309 C 1.006887 2.502944 2.759848 C 0.105984 3.745670 2.640558 C 0.986446 5.011959 2.609129 C 1.947625 4.941920 1.404086 C 2.863961 3.702987 1.545546 C 1.120653 4.844708 0.104625 C 0.246230 3.563758 0.128082 C 1.186395 2.353348 0.246605 C 0.708998 3.636456 1.336921 C 3.117126 2.338791 1.132501 C 2.167537 3.155164 1.781902 C 2.131485 4.519904 1.468166 C 1.270196 2.642927 2.889287 C 4.050375 0.515195 2.529347 C 4.122714 2.921502 0.328152 C 3.044031 5.103723 0.586009 C 4.050714 4.290758 0.053737 C 5.313756 2.127929 0.164937 C 2.958438 6.569 453 0.230696 H 1.932026 2.421564 0.592629 H 4.780249 1.525190 2.157238

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151 H 3.667656 1.403992 3.534005 H 0.396569 1.590792 2.772588 H 1.577643 2.534897 3.699395 H 0.570071 3.786293 3.505342 H 1.554796 5.100818 3.546282 H 0.355022 5.907414 2.533076 H 2.574903 5.842580 1.379617 H 3.574095 3.650763 0.710368 H 3.448526 3.781585 2.474486 H 1.785209 4.828892 0.769283 H 0.482287 5.734056 0.004478 H 0.326993 3.487615 0.797046 H 1.348512 2.744135 1.365047 H 1.373253 4.505750 1.234320 H 1.383308 5.146320 1.950305 H 0.256449 3.049325 2.806718 H 1.662639 2.968835 3.862141 H 1.200 752 1.553982 2.909495 H 3.710203 0.981384 3.463502 H 5.081670 0.831345 2.350639 H 4.812153 4.736035 0.583623 H 5.078628 1.077998 0.350515 H 6.122235 2.161296 0.578760 H 5.718121 2.559285 1.0 86636 H 2.377122 6.719144 0.688734 H 3.951207 6.999276 0.059643 H 2.469093 7.146317 1.022282 C 6.159628 0.707354 1.778115 H 6.580968 1.119593 2.692400 N 1.006197 1.205055 2.977940 O 1.446751 2.145606 3.636429 C 2.457444 2.179621 0.757211 C 1.787215 0.799084 0.474541 C 4.155926 0.626377 0.202649 C 3.949103 1.769886 0.871675 H 2.113941 2.570756 1.725862 H 4.041909 1.271153 1.846847 C 2.718979 0.135557 0.556858 H 2.444274 0.456242 1.564931 H 2.634575 0.952880 0.546604 C 0.284753 0.791786 0.331609 C 4.913109 1.052811 1.430694 H 1.897848 0.235481 1.422651 H 4.715479 0.1 77360 0.287266 H 0.141531 1.561519 0.979181 C 4.976204 2.903900 0.857529 H 4.771768 3.617502 1.665800 H 5.986555 2.508322 1.000732 H 4.974444 3.456836 0.087458 C 2.162233 3.247229 0.305416 H 1.096699 3.501711 0.317835 H 2.713814 4.169425 0.094385 H 2.438013 2.921487 1.314647 C 7.062545 0.193950 0.983207 H 7.861463 0.586860 1.620699 O 7.640043 0.574156 0.105211 C 8.576743 0.044777 0.937036 O 8.963805 0.708890 1.869452 C 9.092298 1.351290 0.637981 H 9.590469 1.388055 0.337569 H 8.280749 2.087016 0.618553 H 9.807457 1.622300 1.414966 H 4.375583 1.719393 2.106253 H 6.5 11495 1.043795 0.564741 C 0.761822 1.679230 1.558314 C 1.560272 0.710562 2.204535 C 3.049519 0.879811 2.370676 H 3.421979 1.681511 1.737995 H 3.280529 1.136012 3.411691 O 3.813435 0.281804 1.974689 C 3.979881 1.377307 2.767569 C 3.549064 1.298731 4.219220 H 4.047652 0.475347 4.742535 H 2.468246 1.148124 4.309962 H 3.815398 2.241396 4.697727 O 4.484466 2.360605 2.276368 H 1.06137 8 0.204578 3.026979 H 0.231061 1.854086 1.952553 H 1.227329 2.491359 1.007351 17 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1729374900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2891361400 a.u Ru 0.867342 0.735130 0.593965 O 1.064713 1.309793 3.236358 O 0.724936 0.848908 2.061841 N 2.343877 2.332670 1.271504 N 3.182551 0.347151 1.650151 C 2.323060 1.044169 0.841410 C 3.064029 2.527373 2.53226 1 C 1.402173 3.304742 0.710119 C 0.100420 3.376866 1.552188 C 0.904708 4.337496 0.886543 C 0.279424 5.744739 0.797912 C 1.016576 5.680831 0.036272 C 2.019030 4.723165 0.645030 C 0.686224 5.167680 1.451696 C 0.061235 3.750342 1.368040 C 1.101723 2.813679 0.724850 C 1.230056 3.818681 0.528194 C 3.824716 0.913981 1.395758 C 3.495483 2.028271 2.191196 C 4.183744 3.225597 1.976610 C 2.439355 1.953308 3.269143 C 3.873215 1.231611 2.619725 C 4.874874 0.979326 0.458035 C 5.193990 3.339138 1.017627 C 5.537667 2.199353 0.285815

PAGE 159

152 C 5.279480 0.219648 0.370336 C 5.862953 4.666 315 0.755358 H 2.036366 2.858495 1.305299 H 3.693417 3.420583 2.504853 H 2.358061 2.629687 3.367850 H 0.331559 2.371943 1.639099 H 0.334387 3.720342 2.570139 H 1.819989 4.377065 1.492032 H 0.065170 6.130133 1.805045 H 0.988811 6.442425 0.333304 H 1.466735 6.680337 0.096820 H 2.961862 4.687578 0.083290 H 2.250141 5.091656 1.655346 H 1.592915 5.141277 2.070760 H 0.016490 5.855171 1.942782 H 0.176343 3.422738 2.381411 H 1.691432 2.825694 0.479178 H 1.954488 4.486522 1.014012 H 3.915382 4.096183 2.570615 H 1.461027 1.675465 2.865499 H 2.333402 2.919838 3.770271 H 2.688 848 1.209040 4.035710 H 3.870131 0.785789 3.617915 H 4.917165 1.376656 2.315735 H 6.335711 2.260333 0.451094 H 5.688067 1.029023 0.247683 H 6.051834 0.057584 1.093751 H 4.431970 0.637482 0.9 23953 H 5.241041 5.275576 0.086840 H 6.840281 4.539470 0.278298 H 6.004729 5.237288 1.679572 C 5.931628 2.424991 0.765725 H 6.258909 3.400032 1.122395 N 0.186078 1.173818 3.209484 O 0.909908 1.338522 4.183144 C 2.246554 1.291094 1.986342 C 1.694319 0.423136 0.811574 C 4.008739 1.064957 0.238671 C 3.776932 1.113600 1.805443 H 1.938035 0.853983 2.947180 H 4.002378 0.099636 2.164575 C 2.596467 0.823690 0.375219 H 2.236610 1.752170 0.836594 H 2.603437 0.073799 1.165849 C 0.164423 0.430840 0.669841 C 4.671270 2.289690 0.332379 H 1.961991 0.611999 1.076897 H 4.642405 0.1 96356 0.032573 H 0.271418 0.473314 1.671927 C 4.679862 2.070651 2.587304 H 4.496972 1.977798 3.665132 H 5.736255 1.847799 2.402939 H 4.520113 3.117317 2.309266 C 1.774127 2.752548 1.970614 H 0.683848 2.818688 2.053728 H 2.198978 3.307619 2.813621 H 2.065875 3.278357 1.054139 C 6.986045 1.358657 0.769288 H 7.594355 1.431936 1.678176 O 7.827190 1.563466 0.394768 C 8.970089 0.849262 0.583418 O 9.608810 1.033844 1.591864 C 9.384499 0.137769 0.493558 H 9.602456 0.375465 1.437244 H 8.598685 0.873912 0.695489 H 10.283414 0.651795 0.152499 H 4.037529 3.176589 0.385898 H 6.5 50195 0.355608 0.728621 C 0.533515 1.550334 0.247149 C 1.220176 1.017008 1.543390 C 2.573541 1.552773 1.938297 H 3.187315 1.831850 1.087013 H 3.090257 0.824057 2.565683 O 2.430895 2.712226 2.814298 C 2.363843 3.929124 2.236046 O 2.413009 4.126264 1.038541 C 2.219518 5.008577 3.286115 H 3.039360 4.947646 4.008978 H 1.286718 4.864932 3.841784 H 2.215472 5.987452 2.805023 H 0.27365 4 2.207799 0.577675 H 1.259331 2.108646 0.341356 H 0.550963 1.076701 2.403094 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1758326000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2884839000 a.u Ru 1.212546 0.642109 0.523215 O 0.139395 2.305466 0.711769 O 0.213485 2.002565 1.442171 N 3.824142 0.424863 0.703930 N 2.935321 1.540521 1.099650 C 2.697255 0.318038 0.519560 C 4.910714 0.270214 1.3971 71 C 3.779816 1.878454 0.547959 C 3.547703 2.557708 1.925877 C 3.429868 4.084665 1.753925 C 4.716946 4.633736 1.106613 C 4.922001 3.969082 0.269732 C 5.078914 2.443970 0.078083 C 3.702318 4.266261 1.168402 C 2.410631 3.695694 0.515758 C 2.608168 2.177516 0.388661 C 2.216673 4.381920 0.853728 C 1.984243 2.530515 1.533627 C 1.157956 2.241042 2.646519 C 0.306121 3.238803 3.121796 C 1.172597 0.885311 3.315345

PAGE 160

153 C 4.249054 1.599277 1.783984 C 2.003615 3.817546 0.969592 C 0.261591 4.515029 2.543811 C 1.124078 4.783211 1.482091 C 2.941273 4.214083 0.147303 C 0.696302 5.562 964 3.059775 H 2.871328 1.787116 1.400634 H 5.768235 0.410451 0.728269 H 5.254116 0.296350 2.268828 H 2.629214 2.155069 2.369718 H 4.378684 2.318669 2.604470 H 3.284308 4.546129 2.739413 H 5.584588 4.440380 1.753680 H 4.642560 5.723117 0.989809 H 5.832044 4.363889 0.740135 H 5.266487 1.949198 1.040692 H 5.943860 2.238190 0.569684 H 3.849210 3.830198 2.166082 H 3.597518 5.351202 1.306746 H 1.559541 3.909290 1.169719 H 1.296738 4.027955 1.325960 H 2.114696 5.465702 0.705284 H 0.335956 3.017378 3.971763 H 0.759971 0.107227 2.662796 H 0.577469 0.904705 4.233183 H 2.187 366 0.569039 3.584418 H 4.099188 1.698605 2.865859 H 4.817198 2.470912 1.445429 H 1.129285 5.776508 1.037893 H 3.425769 5.170053 0.083707 H 2.397835 4.338940 1.090141 H 3.723069 3.469189 0.3 12575 H 1.711150 5.388898 2.679032 H 0.396910 6.568589 2.747849 H 0.755250 5.548901 4.153952 C 6.394720 0.066234 1.573055 H 7.014075 0.492291 2.272960 N 0.639277 2.654248 0.403656 O 1.475907 3.537409 0.516993 C 2.637784 1.332063 0.991795 C 1.805065 0.234025 0.255400 C 4.178522 0.148292 0.291811 C 4.034695 0.662491 1.062583 H 2.244781 1.471730 2.008505 H 3.960356 0.098422 1.851454 C 2.744890 0.180258 0.899471 H 2.685077 0.545272 1.720830 H 2.507932 1.153893 1.329513 C 0.350838 0.633089 0.013529 C 5.187386 0.418202 1.253444 H 1.761485 0.609171 0.957041 H 4.471828 1.1 69053 0.029174 H 0.028169 1.299785 0.779191 C 5.214581 1.566181 1.429612 H 5.054094 2.027742 2.412088 H 6.146110 0.991452 1.475335 H 5.369348 2.371013 0.703652 C 2.624720 2.703302 0.299993 H 1.609547 3.111475 0.253165 H 3.239969 3.423124 0.851334 H 3.013616 2.662123 0.724250 C 7.026074 1.310228 1.023741 H 7.501587 1.881714 1.830358 O 8.035018 0.903781 0.065058 C 8.852345 1.811657 0.534180 O 9.669163 1.418267 1.332567 C 8.691649 3.274863 0.161618 H 8.903176 3.439868 0.901033 H 7.673037 3.630881 0.351350 H 9.394462 3.855139 0.759868 H 4.888720 1.349016 1.739253 H 6.2 92475 1.956793 0.533410 C 0.055773 1.216626 1.406845 C 1.265794 0.482700 2.157504 C 2.404631 1.352676 2.626178 H 2.636235 2.153561 1.925587 H 3.297930 0.745161 2.796819 O 2.141235 1.926334 3.946859 C 1.567671 3.141523 4.020148 O 1.269725 3.826035 3.060390 C 1.341941 3.541210 5.461105 H 2.275619 3.467406 6.027432 H 0.623817 2.857514 5.926787 H 0.956848 4.560756 5.500937 H 0.8066 95 1.166049 2.073105 H 0.368608 2.251942 1.263809 H 0.892557 0.123041 2.993653 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1664527500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2866908700 a.u Ru 1.0499 04 0.806831 0.578464 O 1.101067 0.114027 3.273658 O 0.543012 1.509939 1.875368 N 3.015337 1.997179 1.181679 N 3.236732 0.131343 1.630576 C 2.573617 0.755635 0.822276 C 3.854488 2.007911 2.38 3083 C 2.288064 3.181728 0.721161 C 1.165112 3.564866 1.725365 C 0.344137 4.748539 1.177008 C 1.280623 5.955431 0.962202 C 2.390145 5.576557 0.040965 C 3.217862 4.401667 0.528201 C 1.746355 5.160859 1.379919 C 0.806768 3.945926 1.165115 C 1.654536 2.785337 0.617836 C 0.296834 4.336981 0.162414

PAGE 161

154 C 3.265993 1.566771 1.595207 C 2.413180 2.303438 2.439606 C 2.458275 3.702477 2.376517 C 1.516903 1.649892 3.468928 C 4.221147 0.528910 2.515323 C 4.252912 2.222952 0.826429 C 3.352052 4.379154 1.545437 C 4.264990 3.618548 0.807133 C 5.317293 1.463869 0.063047 C 3.329545 5.88 2891 1.422699 H 2.466359 2.557389 1.342672 H 4.728152 2.652848 2.256270 H 3.285179 2.370270 3.249846 H 0.516172 2.692371 1.885974 H 1.603282 3.831103 2.697514 H 0.436057 5.011259 1.903748 H 1.723984 6.268673 1.918424 H 0.708062 6.811098 0.580620 H 3.055379 6.435713 0.197441 H 4.033731 4.135716 0.157264 H 3.674547 4.700063 1.483363 H 2.525239 4.912540 2.114298 H 1.174584 6.002258 1.795498 H 0.349156 3.652725 2.111128 H 0.982673 3.493222 0.022495 H 0.889830 5.168281 0.566828 H 1.777174 4.274641 3.003410 H 0.514157 2.089876 3.463690 H 1.927150 1.805584 4.475906 H 1.41 7603 0.573781 3.313937 H 4.131080 0.148062 3.536698 H 5.239736 0.324285 2.163849 H 4.998159 4.126740 0.184582 H 6.205954 1.305944 0.689197 H 5.644052 2.028866 0.815413 H 4.972881 0.482792 0. 273729 H 2.840636 6.176104 0.484957 H 4.342262 6.301627 1.407500 H 2.779869 6.347997 2.247133 C 6.055357 1.388740 1.032141 H 6.468688 2.163498 1.675355 N 1.172621 1.086708 2.946803 O 1.823383 1.921830 3.572815 C 2.159957 1.573903 1.584991 C 1.571496 0.391488 0.746210 C 3.998599 0.563740 0.248611 C 3.656762 1.179183 1.660813 H 1.731754 1.555772 2.597685 H 3.702171 0.334855 2.363806 C 2.619057 0.167978 0.365305 H 2.403262 0.785703 1.241999 H 2.616033 0.865486 0.715213 C 0.082731 0.535401 0.416714 C 4.773115 1.484204 0.656223 H 1.623954 0.479970 1.418998 H 4.59520 2 0.337256 0.422485 H 0.424835 0.863418 1.321943 C 4.628042 2.241701 2.180192 H 4.350867 2.556534 3.194153 H 5.650237 1.849470 2.215446 H 4.651431 3.133337 1.545809 C 1.891942 2.967594 0.998 241 H 0.821107 3.196716 0.999266 H 2.390204 3.741383 1.591941 H 2.245871 3.066645 0.034127 C 7.020499 0.315707 0.624688 H 7.671500 0.056210 1.467357 O 7.825790 0.827264 0.469237 C 8.891275 0.133900 0.952510 O 9.499910 0.586340 1.893159 C 9.264384 1.172451 0.273950 H 9.574793 1.003361 0.763623 H 8.424554 1.875462 0.253214 H 10.094170 1.614744 0.825741 H 4.210955 2.334436 1.045006 H 6.504803 0.592896 0.298752 C 0.413562 1.408595 0.811729 C 1.414794 0.701667 1.824659 C 2.741041 1.370872 2.095164 H 3.104791 1.947792 1.249256 H 3.486733 0.633060 2.400998 O 2.636037 2.251714 3.251840 C 2.303643 3.541767 3.027019 O 2.127484 4.022670 1.925787 C 2.173135 4.292622 4.332260 H 3.041464 4.109713 4.972124 H 1.288828 3.933379 4.870456 H 2.066955 5.359348 4.130733 H 0.458768 1.681516 1.404238 H 0.933790 2.280701 0.415056 H 0.901411 0.488487 2.763706 TS17E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1690679000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2821080400 a.u Ru 1.164398 0.503985 0.453596 O 2.848972 0.259803 2.088043 O 0.751551 0.394974 2.634547 N 2.012923 2.144328 1.766149 N 2.080676 0.096035 2.544036 C 1.819272 0.842869 1.424437 C 2.237004 2.3 51160 3.197338 C 1.666947 3.201230 0.812976 C 0.268165 3.793870 1.103807 C 0.102625 4.819300 0.012351 C 0.937718 5.957175 0.007235 C 2.335051 5.370255 0.280334 C 2.698797 4.355442 0.829117

PAGE 162

155 C 2.317524 4.672161 1.657956 C 1.279202 3.518476 1.650903 C 1.714620 2.515249 0.565732 C 0.110703 4.115274 1.360240 C 2.357679 1.310659 2.608744 C 1.451179 2.151701 3.280658 C 1.766834 3.509387 3.406923 C 0.162211 1.616503 3.860970 C 2.579092 0.930184 3.661487 C 3.578280 1.811685 2.109147 C 2.954447 4.043510 2.899608 C 3.848339 3.175221 2.262826 C 4.580878 0.915614 1.416726 C 3.2 59075 5.518618 3.012829 H 2.777413 2.285966 0.756398 H 3.046213 3.063286 3.382279 H 1.327517 2.732893 3.682075 H 0.466374 2.982806 1.131775 H 0.262621 4.277751 2.091209 H 1.098462 5.230448 0 .226933 H 0.935295 6.478873 0.974948 H 0.678816 6.701526 0.757827 H 3.080697 6.176099 0.283462 H 3.704861 3.947417 0.664808 H 2.705623 4.865099 1.804262 H 3.314028 4.279130 1.899120 H 2.064584 5.403686 2.438512 H 1.271449 3.031818 2.632175 H 0.868706 3.326674 1.378138 H 0.378492 4.835275 2.146318 H 1.063849 4.165064 3.916129 H 0.343773 0.967176 4.727339 H 0.395572 1.019633 3.1314 32 H 0.481026 2.435229 4.196930 H 2.092493 0.654976 4.601002 H 3.660643 0.785628 3.783562 H 4.784427 3.569341 1.872806 H 4.878604 0.068076 2.045739 H 5.486770 1.475592 1.166682 H 4.178088 0 .494453 0.488320 H 2.682101 5.987099 3.816652 H 3.011688 6.042204 2.080327 H 4.322492 5.694118 3.209347 N 1.976588 0.319453 3.029287 O 2.277138 0.284417 4.210588 C 5.987118 1.716560 1.356528 H 5.998422 1.772356 2.446404 C 7.003236 2.596821 0.677342 H 6.752345 3.653624 0.831007 H 7.999249 2.446553 1.112278 O 7.034273 2.435992 0.745084 C 7.793569 1.475427 1.349006 O 7.677529 1.321139 2.540459 C 8.759810 0.675281 0.494713 H 9.542220 1.318897 0.076009 H 8.247872 0.180900 0.336895 H 9.226360 0.074204 1.134336 C 2.931293 1.707573 0.148460 C 1.818658 0.765904 0.721299 C 4.047060 0.112548 1.432586 C 4.091432 1.432679 1.143161 H 2.619174 2.754620 0.243748 H 3.789369 1.916152 2.082515 C 2.607636 0.546128 1.006559 H 2.653991 1.166709 0.102266 H 2.120003 1.14 3339 1.781881 C 0.601187 0.548042 0.141388 C 5.094764 0.939736 0.736166 H 1.508708 1.176184 1.689606 H 4.170027 0.263058 2.511799 H 0.888233 0.289853 1.174465 H 5.090187 0.924779 0.353420 C 5.460890 2.005661 0.771271 H 5.400686 3.090886 0.623711 H 6.186313 1.820671 1.572451 H 5.867346 1.566371 0.145406 C 3.287913 1.466512 1.326861 H 2.451903 1.727120 1.984786 H 4.136289 2.091190 1.624984 H 3.558369 0.425434 1.536765 C 0.437236 2.143024 0.207688 C 1.649183 2.266143 0.785718 H 2.543737 2.267320 0.172310 C 1.842815 2.651936 2.226241 H 2.634255 2.055539 2.683081 H 0.915260 2.523861 2.795507 O 2.229856 4.043996 2.215809 C 2.687374 4.655517 3.346521 O 3.007421 5.817953 3.279688 C 2.762943 3.835763 4.620577 H 3.479990 3.012536 4.525893 H 1.795266 3.389677 4.874589 H 3.081773 4.495958 5.427485 H 0.470553 2.254196 0.791509 H 0.328183 2.067102 0.865968 TS18E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1677219000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.282 6465400 a.u Ru 1.243883 0.484271 0.502913 O 2.883569 0.719385 2.290657 O 0.741342 0.698068 2.634557 N 1.990358 1.881219 1.927733 N 2.042911 0.232529 2.499158 C 1.841178 0.622177 1.444224 C 2.12 0605 1.947411 3.384531 C 1.682882 3.030609 1.072792 C 0.242655 3.542418 1.314063

PAGE 163

156 C 0.085222 4.670999 0.315607 C 0.902255 5.836443 0.530121 C 2.343021 5.334219 0.300292 C 2.660761 4.207644 1.311274 C 2.469291 4.804333 1.143961 C 1.485240 3.624164 1.359033 C 1.864126 2.509398 0.363929 C 0.049813 4.132960 1.124302 C 2.354172 1.633718 2.450681 C 1.432440 2.559458 2.972959 C 1.7724 51 3.917677 2.964668 C 0.109650 2.120657 3.559152 C 2.437134 0.488555 3.731591 C 3.620374 2.054364 1.989471 C 3.000076 4.371286 2.476282 C 3.913963 3.420545 2.007241 C 4.644027 1.068212 1.47 1915 C 3.328180 5.844959 2.434626 H 2.942274 2.320833 0.487371 H 2.912647 2.637571 3.687994 H 1.180183 2.284369 3.841911 H 0.455686 2.708500 1.193378 H 0.140713 3.913256 2.344462 H 1.111882 5.020866 0.490320 H 0.797073 6.240459 1.547197 H 0.675934 6.656147 0.164938 H 3.050127 6.159730 0.455700 H 3.693749 3.857057 1.185195 H 2.567795 4.598790 2.335619 H 3.497640 4.473402 1.340805 H 2.252346 5.614837 1.854379 H 1.580932 3.267577 2.389453 H 0.666448 3.322847 1.301015 H 0.186610 4.931125 1.841842 H 1.055544 4.638525 3.351934 H 0.232575 1.735234 4.580496 H 0.355347 1.32 2464 2.972994 H 0.589192 2.960801 3.614515 H 1.875423 0.118479 4.593594 H 3.505408 0.332942 3.929803 H 4.882988 3.751433 1.639878 H 4.878239 0.292800 2.211032 H 5.577804 1.580868 1.223409 H 4.293913 0.550761 0.571275 H 2.717561 6.412393 3.144328 H 3.141741 6.257775 1.434856 H 4.382581 6.027745 2.669344 N 1.929752 0.835658 3.129391 O 2.105168 1.050050 4.317902 C 6.165329 1.642054 1.366433 H 6.197256 1.694556 2.456061 C 7.252276 2.420991 0.672889 H 7.100373 3.497527 0.818815 H 8.233417 2.183408 1.102689 O 7.257860 2.246203 0.748362 C 7.915932 1.210610 1.347150 O 7.773363 1.054248 2.535459 C 8.811317 0.333115 0.491766 H 9.657229 0.904656 0.092369 H 8.265098 0.097324 0.353310 H 9.195806 0.466978 1.124678 C 2.794013 1.484751 0.203510 C 1.778628 0.453613 0.805202 C 4.086455 0.224896 1.469334 C 3.989384 1.317934 1.179393 H 2.390108 2.499082 0.297217 H 3.661990 1.775865 2.122854 C 2.683731 0.784033 1.067535 H 2.764271 1.398289 0.161437 H 2.277 897 1.429009 1.852333 C 0.555171 0.211668 0.051446 C 5.194766 0.954765 0.758120 H 1.460951 0.847961 1.776584 H 4.239345 0.362033 2.546396 H 0.828268 0.090567 1.070828 H 5.173898 0.942566 0.3 31187 C 5.294767 2.009952 0.781386 H 5.132186 3.083252 0.624437 H 6.044722 1.902210 1.574012 H 5.727768 1.599730 0.136549 C 3.151789 1.260907 1.275023 H 2.290840 1.443199 1.926799 H 3.939537 1.953957 1.587850 H 3.510101 0.245692 1.479608 C 0.394026 1.742357 0.403506 C 1.724007 1.668274 0.865018 H 2.504867 1.921585 0.157832 C 2.044251 2.080721 2.282000 H 3.004978 1.670815 2.597930 H 1.263985 1.754724 2.976154 O 2.105168 3.529482 2.270606 C 2.515596 4.230809 3.362760 O 2.543622 5.437330 3.296977 C 2.920740 3.451844 4.600154 H 3.810836 2.841914 4.408005 H 2.129881 2.7 71280 4.933031 H 3.143830 4.166986 5.392314 H 0.382434 1.981602 1.121996 H 0.207142 2.060856 0.614374 TS19E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1732147000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2970255300 a.u Ru 1.467265 0.295853 0.329252 O 2.665347 0.847374 3.914411 O 1.124979 1.034651 2.371088 N 2.500246 1.147373 2.228230 N 1.554788 0.775475 2.676102

PAGE 164

157 C 1.813506 0.110776 1.670344 C 2.551985 1.095466 3.691926 C 2.695357 2.368264 1.444407 C 1.531270 3.366768 1.686570 C 1.684913 4.594311 0.767300 C 3.030615 5.284431 1.070882 C 4.187368 4.293708 0.823837 C 4.032218 3.074 212 1.763681 C 4.151494 3.830611 0.647872 C 2.800339 3.131947 0.957046 C 2.684981 1.918782 0.022413 C 1.652027 4.128504 0.701975 C 0.935499 2.069903 2.606268 C 0.442972 2.181648 2.882005 C 1.034772 3.447221 2.816775 C 1.274036 0.993987 3.313624 C 2.167839 0.364912 3.957862 C 1.721184 3.218839 2.382331 C 0.295402 4.597885 2.523771 C 1.082125 4.462316 2.329317 C 3.228661 3.164105 2.251274 C 0.964079 5.947882 2.414013 H 3.556298 1.244657 0.202706 H 3.546918 1.347387 4.068441 H 1.829927 1.797242 4.131829 H 0.579137 2.857443 1.488863 H 1.522517 3.682877 2.739312 H 0.859 498 5.292431 0.959117 H 3.048569 5.639957 2.111001 H 3.152605 6.167716 0.430109 H 5.145955 4.784559 1.036298 H 4.862882 2.369600 1.623463 H 4.056985 3.407761 2.811525 H 4.985046 3.145029 0.852826 H 4.281034 4.695097 1.313639 H 2.782874 2.793469 1.994518 H 0.689155 3.655947 0.933721 H 1.754243 4.992814 1.372007 H 2.101580 3.535715 3.010955 H 1.193253 0.840283 4.398934 H 0.96314 8 0.064174 2.832576 H 2.333374 1.156364 3.092739 H 1.456801 0.482954 4.779996 H 3.044680 0.990446 4.169684 H 1.681319 5.348051 2.129180 H 3.705936 3.430192 3.204205 H 3.581704 3.882082 1.503 937 H 3.591940 2.173733 1.966211 H 1.902368 5.978066 2.977282 H 1.200178 6.184797 1.368457 H 0.315312 6.747519 2.787129 N 1.557858 0.506375 3.488287 O 0.825692 0.314026 4.071749 C 6.348643 0.497181 1.549709 H 6.433514 0.757881 2.606051 C 7.609035 0.713686 0.754322 H 7.846557 1.783555 0.704237 H 8.464088 0.227701 1.241166 O 7.499011 0.305630 0.614508 C 7.738292 0.978259 1.009554 O 7.520131 1.272048 2.160182 C 8.289619 1.956381 0.011256 H 9.293069 1.659990 0.338537 H 7.649102 2.016333 0.896676 H 8.350136 2.935517 0.464324 C 2.085986 1.532737 0.973894 C 1.505686 0.122 449 1.256670 C 3.917605 0.089084 1.861355 C 3.316461 1.547082 1.919600 H 1.363375 2.290627 1.303867 H 2.903887 1.651720 2.932028 C 2.764867 0.783330 1.269552 H 3.017909 1.094742 0.246804 H 2.609651 1.701573 1.845786 C 0.431071 0.383753 0.306652 C 5.183440 0.063608 1.060978 H 1.086691 0.149423 2.265462 H 4.133876 0.231385 2.887433 H 0.832506 0.560363 0.691245 H 5.121086 0.165903 0.002657 C 4.315178 2.690225 1.726682 H 3.816224 3.661701 1.829893 H 5.107865 2.644074 2.482995 H 4.797896 2.666523 0.744019 C 2.415839 1.807658 0.501710 H 1.509372 1.766936 1.116661 H 2.847855 2.806267 0.628561 H 3.128659 1.088062 0.921648 C 0.348741 1.673757 0.830790 C 1.916232 1.622299 0.710283 H 2.272880 2.195333 0.140071 C 2.691521 2.027584 1.946972 H 3.753213 1.775719 1.829398 H 2.309236 1.559192 2.848323 O 2.567305 3.466793 2.051076 C 2.737706 4.118163 3.238929 O 2.627230 5.321382 3.248157 C 3.052797 3.291724 4.470456 H 3.953392 2.684161 4.326998 H 2.23 7265 2.601560 4.715304 H 3.208195 3.978575 5.302939 H 0.082978 1.829864 1.877454 H 0.015813 2.503711 0.202789 TS20E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1547532600 a.u. M06/SDD/6 311++G(d,p) SCF energy in s olution: 2343.2741231000 a.u Ru 1.377736 0.397376 0.279352

PAGE 165

158 O 0.985535 0.151364 3.782321 O 1.078375 1.375624 2.189364 N 1.847128 1.199831 2.446494 N 1.388562 0.937447 2.611536 C 1.549805 0.091133 1.720440 C 1.685467 1.012284 3.890447 C 1.936184 2.496892 1.765315 C 0.558655 3.208556 1.750060 C 0.646751 4.515421 0.938462 C 1.698819 5.442110 1.580650 C 3.069546 4.734061 1.587789 C 2.9669 77 3.437925 2.427347 C 3.475141 4.403335 0.134064 C 2.423140 3.460725 0.506738 C 2.392589 2.162586 0.325620 C 1.056370 4.174874 0.508039 C 1.353622 2.343046 2.318083 C 0.131977 3.037478 2.41 0229 C 0.116600 4.405266 2.109914 C 1.145182 2.373575 2.874846 C 1.688746 0.518402 3.997985 C 2.554855 3.034033 2.041147 C 1.274228 5.099329 1.751453 C 2.485124 4.397324 1.741222 C 3.913808 2.371512 2.136862 C 1.226898 6.563844 1.383962 H 3.431588 1.807777 0.408675 H 2.499436 1.478906 4.450986 H 0.736541 1.446647 4.235544 H 0.190267 2.540029 1.305473 H 0.232724 3.419947 2.779103 H 0.333805 5.009903 0.944511 H 1.401002 5.705167 2.605848 H 1.764979 6.381928 1.016413 H 3.822179 5.391077 2.043047 H 3.941578 2.934390 2.481510 H 2.670282 3.692950 3.455963 H 4.467344 3.930848 0.116439 H 3.555652 5.334279 0.445113 H 2.709250 3.229772 1.537977 H 0.304588 3.536186 0.984261 H 1.116446 5.094978 1.105666 H 0.829578 4.940245 2.161706 H 1.356004 2.637535 3.920028 H 1.092307 1.284479 2.815511 H 2.004442 2.709320 2.284530 H 0.936476 0.905396 4.690845 H 2.669558 0.906493 4.303102 H 3.404857 4.926954 1.501501 H 4.339782 2.520010 3.138682 H 4.615874 2.81 3935 1.422950 H 3.876301 1.295517 1.952813 H 0.307550 7.037634 1.742369 H 1.264583 6.697236 0.295088 H 2.078408 7.110241 1.804488 N 0.617946 0.959906 3.344497 O 0.154017 1.700036 3.952179 C 6.443085 0.997998 1.766396 H 6.499480 1.042951 2.855324 C 7.702681 1.425869 1.060420 H 7.893419 2.491406 1.238647 H 8.572230 0.884031 1.453428 O 7.625383 1.306929 0.364756 C 7.931818 0.146259 1.013759 O 7.736331 0.088855 2.203776 C 8.525142 0.995852 0.209851 H 9.510200 0.726723 0.188824 H 7.883071 1.271657 0.632567 H 8.638620 1.849541 0.878358 C 2.285015 1.052600 0.695625 C 1.63 8381 0.238151 1.261949 C 4.039130 0.254934 1.892793 C 3.503754 1.209475 1.644090 H 1.606514 1.903895 0.837761 H 3.081829 1.537102 2.603012 C 2.856811 1.179495 1.464913 H 3.097673 1.693868 0. 525487 H 2.647099 1.959432 2.203897 C 0.542618 0.917039 0.464575 C 5.308504 0.620561 1.170893 H 1.257562 0.002802 2.256910 H 4.223852 0.370131 2.967335 H 0.797495 1.143193 0.566319 H 5.275525 0.609511 0.081672 C 4.553510 2.245392 1.238040 H 4.096366 3.236717 1.131034 H 5.335964 2.324276 2.002132 H 5.044197 1.999186 0.290422 C 2.650569 0.973691 0.795183 H 1.757620 0.829161 1.413821 H 3.127780 1.901215 1.129041 H 3.340598 0.152621 1.020844 C 0.416015 1.725973 1.062443 C 2.686804 0.820871 0.742506 H 2.980639 1.676147 0.129524 C 3.502495 0.709284 1.997281 H 4.3229 76 0.004545 1.812340 H 2.889971 0.342145 2.820825 O 4.062502 2.007791 2.277926 C 4.475936 2.360139 3.530997 O 4.940133 3.463940 3.687328 C 4.323911 1.343816 4.645114 H 4.837642 0.405904 4.40 5141 H 3.269801 1.103021 4.822936 H 4.756346 1.771246 5.550149 H 0.523665 1.739576 2.142995 H 0.857535 2.547767 0.509931

PAGE 166

159 TS21E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1609545000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2720807700 a.u Ru 1.573537 0.118488 0.376627 O 0.832992 2.260883 0.023235 O 1.262026 1.555880 2.025973 N 3.141621 0.413451 2.001817 N 1.518512 1.875544 2.102408 C 2.025741 0.844453 1.353738 C 3.316394 1.002062 3.331987 C 3.830312 0.800607 1.554565 C 3.328808 2.043273 2.335114 C 4.026085 3.314989 1.808304 C 5.552492 3.177855 1.967078 C 6.036543 1.952187 1.166276 C 5.362732 0.685892 1.742225 C 5.665480 2.133246 0.323550 C 4.122636 2.248133 0.475606 C 3.523315 0.918782 0.048621 C 3.673779 3.495750 0.319451 C 0.350773 2.676851 1.884273 C 0.866297 2.2 66966 2.472090 C 1.998108 3.064783 2.294098 C 0.943551 1.018210 3.320859 C 2.373016 2.206490 3.261554 C 0.444019 3.909038 1.211164 C 1.950311 4.267561 1.576983 C 0.719784 4.675899 1.059858 C 1.753542 4.452014 0.682898 C 3.198552 5.092303 1.367382 H 4.113886 0.127318 0.433127 H 4.355740 1.290172 3.509672 H 3.019409 0.290224 4.114796 H 2.242949 2.133687 2.218014 H 3.540145 1.920143 3.407564 H 3.670793 4.181872 2.380966 H 5.822104 3.067991 3.027490 H 6.050176 4.087057 1.603429 H 7.125725 1.851485 1.264811 H 5.726044 0.215448 1.230050 H 5.628320 0.587691 2.805714 H 6.044103 1.285962 0.912236 H 6.153291 3.037283 0.715285 H 3.873404 2.376551 1.536021 H 2.603271 3.676096 0.214913 H 4.190569 4.380868 0.077741 H 2.940119 2.744652 2.734286 H 0.431899 1.162149 4.282165 H 0.473821 0.156689 2.837632 H 1.983648 0.761306 3.540826 H 1.768491 2.335857 4.163680 H 2.912209 3.145259 3.075638 H 0.654809 5.621633 0.525300 H 2.101102 5.289628 1.301962 H 1.639 422 4.836654 0.336803 H 2.541632 3.696351 0.673785 H 3.835899 5.088596 2.258436 H 3.799331 4.693711 0.539487 H 2.956286 6.132089 1.125534 N 0.882911 2.533571 1.274518 O 0.587850 3.627850 1.7 24010 C 6.603945 0.641975 1.567215 H 6.709775 0.797486 2.642340 C 7.880402 0.250192 0.870770 H 8.217861 0.732378 1.223507 H 8.684922 0.958134 1.107466 O 7.736653 0.093673 0.545558 C 7.868658 1.141829 1.409516 O 7.645545 0.948118 2.580077 C 8.311759 2.483100 0.855127 H 9.337349 2.430533 0.471352 H 7.661932 2.816567 0.040146 H 8.279328 3.206920 1.669740 C 2.226643 1.999022 0.366483 C 1.722224 0.743515 1.134988 C 4.132653 1.111678 1.715707 C 3.421665 2.437453 1.254842 H 1.476052 2.791731 0.379570 H 2.965604 2.855820 2.163135 C 3.049509 0.010385 1.506316 H 3.342003 0.6 54641 0.683966 H 2.927201 0.627053 2.388404 C 0.784809 0.242710 0.452525 C 5.406782 0.771576 0.989118 H 1.261049 1.085381 2.069485 H 4.374083 1.201771 2.781964 H 0.991583 0.433016 0.595317 H 5.324618 0.588894 0.082017 C 4.335028 3.522384 0.681396 H 3.757134 4.419231 0.427843 H 5.097171 3.814878 1.413809 H 4.858164 3.194933 0.223065 C 2.577649 1.733808 1.104167 H 1.670715 1.519275 1.677854 H 3.040294 2.615436 1.559825 H 3.268330 0.892417 1.239802 C 0.243649 1.305811 1.180314 C 2.013263 1.370474 1.432561 H 2.124400 2.413084 1.114242 C 2.337470 1.225184 2.891848 H 3.4 37854 1.204063 2.971520 H 1.946827 0.294397 3.310125 O 1.822483 2.370885 3.605933 C 1.952752 2.492590 4.958831 O 1.495437 3.472660 5.494887 C 2.663522 1.380277 5.705765 H 3.678268 1.222623 5 .323985 H 2.126719 0.429952 5.606883

PAGE 167

160 H 2.712442 1.656715 6.759153 H 0.345509 1.308633 2.263298 H 0.132631 2.278559 0.719434 TS22E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.15253528000 a.u. M06/SDD/6 311++G(d ,p) SCF energy in solution: 2343.27276572000 a.u Ru 1.386850 0.302974 0.229285 O 2.681949 1.978727 3.161833 O 0.902811 1.130901 2.170674 N 1.659749 0.880993 2.576825 N 1.181458 1.259516 2.526670 C 1.424395 0.160313 1.741379 C 1.368880 0.580064 3.980501 C 1.821387 2.222898 2.005807 C 0.458641 2.956845 1.920386 C 0.633240 4.319873 1.222198 C 1.626685 5.177581 2.031591 C 2.984085 4.448961 2.114577 C 2.794064 3.092234 2.832991 C 3.523604 4.221937 0.686527 C 2.530691 3.349629 0.125996 C 2.403810 1.988306 0.588923 C 1.176427 4.086504 0.201763 C 1.237897 2.635683 2.115912 C 0.052 017 3.391041 2.049689 C 0.131857 4.726946 1.633985 C 1.292441 2.834365 2.462192 C 1.363245 0.954612 3.963492 C 2.491696 3.245236 1.878117 C 1.347248 5.333638 1.313520 C 2.517044 4.578413 1.4 61907 C 3.801335 2.525309 2.125348 C 1.405779 6.759594 0.818894 H 3.422937 1.600463 0.734866 H 2.127570 0.995053 4.648788 H 0.391713 0.991128 4.270552 H 0.254370 2.336741 1.361914 H 0.042210 3.096156 2.928903 H 0.339564 4.827180 1.174488 H 1.233154 5.366822 3.040724 H 1.756225 6.156112 1.550599 H 3.694948 5.056962 2.689514 H 3.756320 2.572407 2.935261 H 2.404436 3.266760 3.847339 H 4.507028 3.733033 0.725400 H 3.669636 5.190837 0.188627 H 2.929092 3.201711 1.133329 H 0.457561 3.509426 0.795226 H 1.303705 5.048524 0.715877 H 0.786606 5.306330 1.563542 H 1.605357 3.2 64869 3.422672 H 1.274313 1.748859 2.576451 H 2.069336 3.090230 1.733402 H 0.555483 1.391367 4.557205 H 2.315076 1.371107 4.318167 H 3.478917 5.042699 1.254350 H 4.110362 2.635191 3.173885 H 4.600075 2.953718 1.511706 H 3.746410 1.455363 1.910788 H 0.491360 7.307974 1.066460 H 1.525261 6.792092 0.271791 H 2.255037 7.299560 1.252102 N 1.451791 2.019091 2.968076 O 0.704941 2.831392 3.509179 C 6.462777 0.617518 2.042778 H 6.493406 0.462370 3.122581 C 7.751940 1.123293 1.450621 H 7.967637 2.133613 1.819529 H 8.595187 0.492401 1.758948 O 7.709257 1.261251 0.025784 C 7.994337 0.222577 0.812353 O 7.824097 0.381401 1.997000 C 8.534189 1.062648 0.212228 H 9.516341 0.900855 0.247185 H 7.863378 1.461072 0.555349 H 8.639036 1.788247 1.019100 C 2.284474 1.103552 0.547418 C 1.651683 0.090064 1.308521 C 4.036260 0.060028 1.984300 C 3.481794 1.447506 1.473679 H 1.584876 1.949568 0.537911 H 3.038986 1.930992 2.354377 C 2.884252 0.952078 1.692333 H 3.16 2536 1.610202 0.858584 H 2.674276 1.603896 2.546703 C 0.599701 0.919230 0.598551 C 5.332682 0.392436 1.367206 H 1.211012 0.309350 2.225280 H 4.192896 0.135345 3.066957 H 0.872444 1.266750 0. 393218 H 5.326202 0.579247 0.293506 C 4.521619 2.417710 0.909605 H 4.048791 3.364342 0.620883 H 5.285887 2.646090 1.661783 H 5.036670 2.018816 0.029434 C 2.679892 0.791506 0.904580 H 1.798993 0.545700 1.508256 H 3.159833 1.656354 1.374830 H 3.377014 0.050868 0.981572 C 0.345750 1.667529 1.282263 C 2.655833 0.941610 0.724639 H 2.838636 1.882294 0.198417 C 3.554304 0.770006 1.91409 6 H 4.563947 0.542071 1.527463 H 3.242896 0.055741 2.552998 O 3.590509 2.032351 2.615435 C 4.077201 2.123645 3.889013

PAGE 168

161 O 4.064709 3.204615 4.427133 C 4.603626 0.860707 4.541043 H 5.405107 0. 409572 3.945191 H 3.819924 0.102589 4.646003 H 4.989208 1.125327 5.525943 H 0.486830 1.535991 2.351221 H 0.752781 2.572913 0.846926 9E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1693277000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2829724700 a.u Ru 1.174888 0.423631 0.496433 O 2.761181 0.272115 2.265517 O 0.630407 0.444320 2.644440 N 2.171608 2.007854 1.711551 N 2.325852 0.057319 2.428922 C 1.965176 0.715950 1.351608 C 2.514491 2.184817 3.122887 C 1.813428 3.090716 0.791887 C 0.434202 3.699373 1.136422 C 0.049617 4.752575 0.076750 C 1.105809 5.875815 0.069114 C 2.4862 27 5.275155 0.267847 C 2.862721 4.230085 0.808488 C 2.422863 4.609766 1.659781 C 1.369712 3.470269 1.651176 C 1.815846 2.432745 0.601292 C 0.003823 4.078437 1.310324 C 2.664473 1.452635 2.42 3072 C 1.885723 2.344530 3.185090 C 2.255482 3.693550 3.220126 C 0.673748 1.874233 3.956771 C 2.902907 0.757077 3.523654 C 3.826636 1.894340 1.755995 C 3.377258 4.171387 2.537245 C 4.153925 3.252396 1.823283 C 4.714314 0.944170 0.982158 C 3.733859 5.639030 2.550747 H 2.869950 2.198178 0.822104 H 3.332275 2.898592 3.254452 H 1.647031 2.550049 3.690102 H 0.312987 2.900353 1.168076 H 0.464887 4.161761 2.133854 H 0.934207 5.173014 0.326300 H 1.136081 6.375695 1.047851 H 0.838529 6.640535 0.672583 H 3.243840 6.069847 0.270995 H 3.858343 3.812169 0.608558 H 2.901934 4.71 8862 1.793581 H 3.406843 4.208195 1.935816 H 2.161024 5.363395 2.416176 H 1.328840 3.011846 2.644923 H 0.771632 3.298815 1.325782 H 0.284170 4.818964 2.072656 H 1.646872 4.388356 3.794836 H 0.959275 1.337909 4.871571 H 0.055009 1.188601 3.368299 H 0.053830 2.723053 4.260466 H 2.493910 0.455576 4.491447 H 3.991807 0.618592 3.556119 H 5.043904 3.600866 1.303366 H 4.993085 0.066167 1.576444 H 5.637584 1.446589 0.678872 H 4.225098 0.568338 0.075889 H 3.305691 6.148704 3.419948 H 3.352505 6.142245 1.652808 H 4.819109 5.787379 2.568599 N 1.825040 0.397424 3.131889 O 2.03 4400 0.450330 4.332522 C 6.110136 1.540766 1.091720 H 6.155509 1.607965 2.180066 C 7.145726 2.365295 0.373005 H 6.949069 3.434177 0.521907 H 8.146006 2.172488 0.780470 O 7.126295 2.188077 1.047627 C 7.825438 1.189665 1.662817 O 7.665350 1.027041 2.848004 C 8.784389 0.359518 0.829288 H 9.606672 0.974305 0.445088 H 8.280000 0.102478 0.025205 H 9.197810 0.416890 1.473349 C 2.8604 06 1.754028 0.021029 C 1.814354 0.756346 0.624507 C 4.102023 0.028399 1.241465 C 4.067585 1.520616 0.969882 H 2.504434 2.784092 0.140337 H 3.780341 1.980636 1.925351 C 2.672710 0.522965 0.85 0196 H 2.720961 1.116480 0.071884 H 2.241250 1.165037 1.623643 C 0.567081 0.513176 0.187965 C 5.165998 0.799136 0.506054 H 1.531100 1.136761 1.612526 H 4.261229 0.185325 2.314911 H 0.810445 0.289203 1.239220 H 5.129859 0.772562 0.582717 C 5.395435 2.157610 0.554448 H 5.281596 3.240329 0.420944 H 6.156849 1.998241 1.327188 H 5.787799 1.745282 0.380680 C 3.174953 1.543610 1.468471 H 2.305593 1.769415 2.095140 H 3.980884 2.211924 1.788788 H 3.489275 0.519276 1.698416 C 0.390806 1.940751 0.002699 C 1.478665 2.023891 0.822970 H 2.469009 2.098166 0.387087 C 1.359950 2.48 2905 2.252520

PAGE 169

162 H 2.142635 2.042140 2.871542 H 0.379712 2.226796 2.667089 O 1.521688 3.920732 2.222930 C 1.669532 4.638482 3.372677 O 1.801341 5.836262 3.289482 C 1.659618 3.886360 4.690279 H 2.512730 3.202595 4.765704 H 0.752902 3.283126 4.807840 H 1.716980 4.617805 5.496708 H 0.603872 2.103952 0.402780 H 0.489157 1.943133 1.072887 10E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1824128100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.3053691300 a.u Ru 1.411218 0.371823 0.374214 O 3.278652 0.847851 2.686528 O 1.092952 0.870010 2.444727 N 2.186978 1.249975 2.281389 N 1.423264 0.770834 2.622923 C 1.670968 0.160707 1.652607 C 2.122320 1.173036 3.743560 C 2.319702 2.499881 1.533237 C 1.044255 3.371481 1.689454 C 1.155206 4.637744 0.819060 C 2.391504 5.448606 1.258265 C 3.659 106 4.583746 1.097395 C 3.542281 3.327679 1.991146 C 3.801131 4.163513 0.379615 C 2.560401 3.341376 0.822073 C 2.502749 2.082633 0.063130 C 1.300184 4.213764 0.655206 C 1.084272 2.159355 2.4 73346 C 0.243652 2.574513 2.684637 C 0.545534 3.937111 2.552879 C 1.341542 1.620619 3.099767 C 1.880840 0.324642 3.957588 C 2.105881 3.105799 2.231923 C 0.430141 4.887657 2.249228 C 1.753091 4.450714 2.108248 C 3.564907 2.711062 2.143841 C 0.078668 6.345968 2.073001 H 3.463692 1.540497 0.034652 H 3.047483 1.525527 4.207049 H 1.291683 1.781091 4.127468 H 0.168328 2.780894 1.392858 H 0.909554 3.650494 2.744142 H 0.249409 5.244650 0.948419 H 2.280984 5.772661 2.302893 H 2.479450 6.358249 0.649501 H 4.541077 5.159380 1.407036 H 4.449988 2.714410 1.915390 H 3.435996 3.6 31037 3.043138 H 4.712819 3.568864 0.524181 H 3.898554 5.055741 1.013591 H 2.687191 3.061935 1.868099 H 0.411465 3.659879 0.983930 H 1.377001 5.102188 1.296635 H 1.574847 4.259022 2.698130 H 1.596990 1.767646 4.157701 H 1.055406 0.575364 2.969358 H 2.258141 1.797286 2.526521 H 1.121813 0.537752 4.715342 H 2.800612 0.855496 4.234766 H 2.532987 5.177823 1.892715 H 4.029291 2.706000 3.139478 H 4.122168 3.428465 1.533772 H 3.707598 1.717046 1.711633 H 0.934721 6.559815 2.426730 H 0.132172 6.637251 1.016382 H 0.773595 6.993301 2.620216 N 2.156188 1.052836 3.195862 O 1.986281 1.407545 4.358170 C 6.346588 0.665134 1.779326 H 6.392506 0.782083 2.863416 C 7.603971 1.072298 1.057164 H 7.776724 2.149044 1.176683 H 8.479510 0.567338 1.484436 O 7.538226 0.872871 0.359568 C 7.870707 0.315803 0.941587 O 7.688725 0.441269 2.128458 C 8.474026 1.402313 0.070553 H 9.453111 1.097483 0.317099 H 7.830560 1.637513 0.782957 H 8.602948 2.291146 0.688552 C 2.257 845 1.542334 0.797503 C 1.565532 0.225594 1.241302 C 3.953803 0.111932 1.933289 C 3.454063 1.601082 1.784869 H 1.585138 2.389824 0.985451 H 3.017334 1.861835 2.758498 C 2.757179 0.752547 1.4 22277 H 3.012927 1.216530 0.460319 H 2.523340 1.572563 2.109381 C 0.479044 0.314147 0.323555 C 5.224464 0.228542 1.200867 H 1.125749 0.414393 2.225900 H 4.124236 0.085052 2.998528 H 0.867917 0.516003 0.674681 H 5.201804 0.145836 0.114489 C 4.536772 2.641503 1.490258 H 4.105459 3.649317 1.450298 H 5.299776 2.639898 2.277806 H 5.047667 2.459253 0.538958 C 2.664925 1.586085 0.683885 H 1.787351 1.513222 1.335284 H 3.168077 2.528969 0.923679 H 3.345988 0.773294 0.961349

PAGE 170

163 C 0.285775 1.597255 0.883465 C 1.854531 1.540705 0.814095 H 2.241687 2.138701 0.004968 C 2.573570 1.9 23696 2.090452 H 3.613877 1.588738 2.060802 H 2.091416 1.503310 2.974539 O 2.525196 3.372682 2.147370 C 3.053762 4.063012 3.194889 O 3.015362 5.270869 3.168286 C 3.651924 3.268555 4.340041 H 4.448157 2.598946 3.997456 H 2.894757 2.642961 4.826192 H 4.056418 3.972871 5.067329 H 0.010899 1.745106 1.923827 H 0.027759 2.437283 0.259511 B3LYP/SDD/6 31G(d) SCF energy in gas p hase : 2344.178730860 0 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.3023534600 a.u Ru 1.518338 0.174100 0.396416 O 0.654235 2.496999 2.369045 O 1.644415 0.539255 2.519479 N 2.553819 0.675186 2.270009 N 1.271592 1.073855 2.548863 C 1.725630 0.181052 1.615994 C 2.542384 0.516787 3.727016 C 3.047834 1.867696 1.584359 C 2.157593 3.096371 1.910262 C 2.642268 4.326883 1.120635 C 4.107477 4.632302 1.490637 C 4.987492 3.412555 1.148664 C 4.509827 2.195720 1.972624 C 4.873579 3.105152 0.359628 C 3.397423 2.789080 0.728415 C 2.982181 1.548110 0.081826 C 2.529713 4.017423 0.382814 C 0.528528 2.289 744 2.356686 C 0.861363 2.290743 2.591514 C 1.568811 3.484108 2.407685 C 1.592534 1.070568 3.103674 C 1.881592 0.857395 3.879148 C 1.208224 3.491383 2.063186 C 0.934362 4.673193 2.036693 C 0.456210 4.657388 1.889555 C 2.718497 3.578390 1.990408 C 1.724406 5.938301 1.798117 H 3.714714 0.733330 0.135890 H 3.552750 0.550994 4.143439 H 1.949943 1.312394 4.198444 H 1.116441 2.863279 1.650981 H 2.191160 3.301879 2.989490 H 2.009330 5.187716 1.372911 H 4.191243 4.871416 2.560508 H 4.457388 5.514169 0.937981 H 6.033386 3.626275 1.404802 H 5.144576 1.320717 1.778030 H 4.585 381 2.424112 3.045759 H 5.521604 2.258439 0.625465 H 5.222395 3.968458 0.942799 H 3.335407 2.577580 1.799100 H 1.490556 3.826201 0.661718 H 2.868098 4.880247 0.972237 H 2.644692 3.482827 2.5 69789 H 1.646572 1.089665 4.201156 H 1.102744 0.138301 2.817257 H 2.622930 1.044141 2.735927 H 1.117487 0.885469 4.660907 H 2.613880 1.647783 4.088085 H 0.974927 5.579128 1.634655 H 3.127633 3.934327 2.945843 H 3.031394 4.292776 1.222059 H 3.187715 2.616703 1.769543 H 2.688269 5.913043 2.316621 H 1.929396 6.077089 0.728630 H 1.176240 6.823382 2.138628 N 1.252892 1.664656 3.074777 O 1.497895 1.824590 4.267765 C 6.352432 0.089907 1.662503 H 6.451841 0.009593 2.746396 C 7.618673 0.201531 0.900965 H 7.908935 1.250814 1.036112 H 8.450731 0.403187 1.283653 O 7.482784 0.0 45997 0.516590 C 7.659739 1.157225 1.135244 O 7.428895 1.230121 2.318152 C 8.160743 2.327428 0.309032 H 9.179817 2.146242 0.052307 H 7.520928 2.509283 0.559995 H 8.167357 3.209089 0.950277 C 2.021438 1.832723 0.779412 C 1.488350 0.462618 1.282789 C 3.899249 0.623336 1.894394 C 3.240133 2.043934 1.716645 H 1.270062 2.601354 0.981260 H 2.809911 2.292951 2.696029 C 2.783764 0.378113 1.457733 H 3.054924 0.846176 0.501879 H 2.659048 1.193511 2.178106 C 0.459946 0.240069 0.412183 C 5.169566 0.391798 1.120430 H 1.059679 0.637138 2.274721 H 4.129346 0.482485 2.957437 H 0.8 71398 0.442113 0.576421 H 5.096316 0.441700 0.034104 C 4.193462 3.183181 1.350000 H 3.650841 4.134421 1.290257 H 4.975858 3.296330 2.110238 H 4.692110 3.022598 0.388159

PAGE 171

164 C 2.353817 1.881546 0.719176 H 1.447195 1.747991 1.320355 H 2.779541 2.853579 0.990815 H 3.071881 1.112659 1.028652 C 0.137859 1.579735 1.036857 C 1.692936 1.762052 0.887352 H 1.939745 2.445568 0.081489 C 2.4363 38 2.169088 2.143398 H 3.517481 2.045637 1.995761 H 2.127197 1.577539 3.004167 O 2.148025 3.575890 2.343570 C 2.527564 4.231818 3.473971 O 2.289469 5.413298 3.563423 C 3.221192 3.433153 4.56 1265 H 4.112748 2.921100 4.183325 H 2.556406 2.664542 4.971556 H 3.506936 4.121329 5.357140 H 0.122886 1.615909 2.096387 H 0.327649 2.401202 0.486611 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344 .1779675800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.3002871900 a.u Ru 1.537441 0.265290 0.367662 O 0.554149 0.465574 3.723316 O 1.465779 1.049911 2.394045 N 2.543757 1.084247 2.219935 N 1.567662 0.828730 2.638854 C 1.853887 0.061474 1.641717 C 2.570299 1.021682 3.683979 C 2.753222 2.313894 1.454895 C 1.583316 3.307659 1.687054 C 1.756788 4.550520 0.793046 C 3.094093 5.237057 1.139078 C 4.257667 4.251522 0.903324 C 4.081069 3.016391 1.817533 C 4.257299 3.811144 0.575387 C 2.914951 3.115822 0.925609 C 2.778774 1.882136 0.017932 C 1.759801 4.107708 0.683087 C 0.963011 2.1 29297 2.552457 C 0.412993 2.262668 2.830261 C 0.989168 3.534774 2.747489 C 1.261197 1.095026 3.282961 C 2.165944 0.435036 3.932710 C 1.763134 3.266406 2.315840 C 0.236712 4.671526 2.436287 C 1.139483 4.516338 2.244483 C 3.270818 3.192170 2.195781 C 0.889014 6.027660 2.306033 H 3.661062 1.220804 0.180529 H 3.561308 1.260455 4.078845 H 1.848603 1.728245 4.116667 H 0.636899 2.800999 1.458821 H 1.550085 3.605525 2.744604 H 0.926270 5.244883 0.976216 H 3.087718 5.575357 2.185038 H 3.229719 6.130783 0.515768 H 5.210417 4.739521 1.146471 H 4.916091 2.315132 1.686264 H 4.0 80056 3.332654 2.871020 H 5.097505 3.130028 0.769311 H 4.400969 4.685781 1.224866 H 2.916079 2.803257 1.971071 H 0.803957 3.638242 0.946950 H 1.877568 4.981404 1.338028 H 2.054595 3.639093 2 .941622 H 1.245894 1.011413 4.378765 H 0.914734 0.140951 2.880644 H 2.306765 1.231458 2.989803 H 1.441406 0.551785 4.743227 H 3.032350 1.072323 4.152281 H 1.749555 5.392071 2.033422 H 3.743789 3.449372 3.153349 H 3.639414 3.908113 1.454058 H 3.623764 2.198150 1.910733 H 1.830431 6.075166 2.862795 H 1.115455 6.254542 1.256141 H 0.233552 6.824330 2.673865 N 1.003213 0.692603 3.566049 O 1.040576 1.527438 4.465501 C 6.313581 0.460376 1.406610 H 6.420055 0.720169 2.461191 C 7.559568 0.669682 0.587004 H 7.800912 1.738343 0.530039 H 8.421435 0.180839 1.058671 O 7.42141 5 0.259084 0.778469 C 7.645766 1.027297 1.174502 O 7.402530 1.323082 2.319570 C 8.212835 2.005324 0.162298 H 9.224089 1.712928 0.143867 H 7.590064 2.059816 0.736039 H 8.259009 2.986041 0.636 215 C 2.026206 1.541405 0.913754 C 1.461405 0.127783 1.215152 C 3.886645 0.113727 1.765539 C 3.276899 1.567901 1.832416 H 1.308717 2.300353 1.253011 H 2.886842 1.674181 2.853563 C 2.728164 0.769090 1.201539 H 2.958640 1.081694 0.174076 H 2.591061 1.685802 1.784241 C 0.366080 0.389225 0.298401 C 5.137022 0.032966 0.940144 H 1.083213 0.139525 2.239777 H 4.125833 0.201834 2.787949 H 0.743515 0.545210 0.711675 H 5.053246 0.195877 0.122186

PAGE 172

165 C 4.262638 2.717584 1.613184 H 3.758898 3.685616 1.724591 H 5.071781 2.679700 2.352226 H 4.723809 2.693934 0.620232 C 2.324329 1.809 004 0.569849 H 1.407132 1.756254 1.167304 H 2.745074 2.810537 0.709944 H 3.035975 1.093448 0.998173 C 0.388694 1.696738 0.815282 C 1.965294 1.648498 0.753771 H 2.349976 2.238500 0.072593 C 2.694744 2.008044 2.031541 H 3.763345 1.774219 1.935182 H 2.273310 1.480307 2.882735 O 2.557523 3.441561 2.193911 C 2.619590 4.042492 3.415857 O 2.497913 5.243863 3.467700 C 2.835679 3.168158 4.635887 H 3.747923 2.567906 4.542682 H 2.001064 2.473172 4.782303 H 2.920395 3.821394 5.504798 H 0.087953 1.877365 1.845916 H 0.082388 2.503290 0.146136 TS24E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1436356700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2680709400 a.u Ru 1.457621 0.063378 0.557292 O 3.728916 0.769540 2.365830 O 1.996066 0.573806 2.553513 N 2.144703 0.042758 2.269448 N 0.311825 1.141259 2.304431 C 1.173964 0.467766 1.471050 C 2.033453 0.316433 3.685746 C 3.147508 0.975562 1.759169 C 2.786219 2.424030 2.178157 C 3.809294 3.414266 1.589660 C 5.222896 3.063449 2.095801 C 5.580864 1.627524 1.660963 C 4.567076 0.644238 2.288712 C 5.533632 1.531834 0.120745 C 4.104091 1.868057 0.382272 C 3.140882 0.835396 0.232724 C 3.761305 3.306694 0.054899 C 0.91 7851 1.820152 2.009024 C 2.127473 1.094827 1.958315 C 3.314329 1.776746 1.665081 C 2.201723 0.365146 2.343151 C 0.657919 0.989463 3.735198 C 0.933472 3.229465 1.946250 C 3.337530 3.163939 1. 482315 C 2.144530 3.872114 1.659950 C 0.281166 4.064899 2.291863 C 4.621707 3.876827 1.129462 H 3.571368 0.174558 0.002013 H 2.843309 0.997175 3.975854 H 2.092754 0.569487 4.325321 H 1.777800 2.656497 1.812947 H 2.769513 2.504322 3.274641 H 3.545791 4.433368 1.903140 H 5.269825 3.153244 3.190773 H 5.954087 3.772913 1.685925 H 6.587533 1.373430 2.017831 H 4.821511 0.391672 2.02703 9 H 4.607324 0.724885 3.385249 H 5.818492 0.526053 0.213210 H 6.260036 2.231617 0.315545 H 4.081241 1.808382 1.472494 H 2.769145 3.588070 0.307638 H 4.479622 4.006485 0.394107 H 4.243011 1. 210874 1.615132 H 1.304729 0.925913 2.071704 H 3.076434 0.845223 1.897150 H 2.322973 0.456590 3.431652 H 0.095974 0.372758 4.240133 H 0.680382 1.964964 4.229549 H 2.157534 4.958961 1.599951 H 1.218628 3.525324 2.142257 H 0.240022 4.367364 3.347327 H 0.317587 4.988084 1.704039 H 5.493337 3.346125 1.525477 H 4.749306 3.942741 0.040719 H 4.633919 4.899902 1.520367 N 3.126381 0.102398 3.030336 O 3.527285 0.544859 4.102048 C 5.662906 2.133937 1.994159 H 5.823265 2.639996 2.947020 C 6.918858 1.651647 1.314255 H 7.462299 0.959450 1.967721 H 7.602395 2.482446 1.097078 O 6.643409 0.888771 0.130489 C 6.427426 1.475215 1.075479 O 5.936132 0.807626 1.959027 C 6.844233 2.920675 1.263012 H 7.920474 3.044916 1.098141 H 6.318147 3.579257 0.564132 H 6.603650 3.21 1349 2.285734 C 0.855133 3.100175 1.985781 C 0.726536 1.533123 2.029098 C 3.137601 2.313688 2.193873 C 2.286101 3.417686 1.487179 H 0.845146 3.388566 3.047236 H 2.588867 4.398141 1.879813 C 2.198762 1.071084 2.301833 H 2.508385 0.310920 1.574853 H 2.291901 0.605357 3.289070 C 0.184959 0.839841 0.790506 C 4.428558 1.939992 1.523350

PAGE 173

166 H 0.071464 1.285342 2.865202 H 3.356919 2.677207 3.205774 H 0.904434 0.841838 0.035524 H 4.319177 1.405842 0.580659 C 2.440509 3.486633 0.037308 H 1.814776 4.283894 0.452593 H 3.477837 3.707389 0.313288 H 2.158261 2.554715 0.534943 C 0.28 4059 3.859190 1.313383 H 1.228190 3.643526 1.821874 H 0.112375 4.942017 1.362693 H 0.402417 3.581948 0.260904 C 0.253624 1.478772 1.535495 C 1.038507 1.994532 1.629900 C 1.521909 3.194106 0. 844826 H 2.489767 3.003818 0.377250 H 0.804923 3.473123 0.073904 O 1.804119 4.313059 1.714212 C 0.856296 5.163884 2.198655 O 1.218634 6.092502 2.879750 C 0.603813 4.903791 1.877231 H 0.788007 4.756504 0.808826 H 0.951277 4.002930 2.393843 H 1.178444 5.760664 2.230579 H 0.948580 1.834785 0.782016 H 0.689263 0.998028 2.401642 H 1.576594 1.856788 2.562427 TS25E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1616613700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2889001600 a.u Ru 1.335821 0.328813 0.595050 O 3.261844 3.051260 2.622445 O 1.443241 2.031076 1.975776 N 2.496452 1.378768 1.414 916 N 0.725850 2.513987 0.799268 C 1.404075 1.326468 0.626321 C 2.695029 2.650863 2.109645 C 3.327805 0.195478 1.618832 C 2.888519 0.521211 2.924011 C 3.701252 1.814328 3.118235 C 5.201737 1.465595 3.197540 C 5.637509 0.760829 1.896120 C 4.833093 0.545079 1.718262 C 5.376226 1.695575 0.699596 C 3.863414 2.040172 0.612025 C 3.099679 0.720960 0.406036 C 3.436212 2.741462 1.917603 C 0.670653 2.767637 0.567783 C 1.631333 2.108754 1.369826 C 2.986643 2.371644 1.150011 C 1.214515 1.180416 2.489207 C 1.388753 3.393369 1.793106 C 1.069853 3.776127 0.330226 C 3.417734 3.298205 0.191517 C 2.440887 3.999121 0.519247 C 0.084472 4.687175 1.030613 C 4.888404 3.578931 0.015044 H 3.526768 0.207115 0.491761 H 3.573239 3.166725 1.706714 H 2.846068 2.499902 3.183873 H 1.816856 0.749320 2.861016 H 3.032056 0.153092 3.780427 H 3.383957 2.303951 4.048490 H 5.394499 0.816766 4.064002 H 5.792562 2.379487 3.344972 H 6.705749 0.513901 1.948201 H 5.147393 1.078 603 0.812980 H 5.013697 1.210177 2.575501 H 5.708107 1.222981 0.233840 H 5.953793 2.623303 0.811930 H 3.719121 2.717500 0.226133 H 2.375515 3.014618 1.872336 H 4.000406 3.676957 2.027823 H 3.729466 1.854616 1.753202 H 0.684703 0.295082 2.124819 H 2.088514 0.842703 3.052173 H 0.541990 1.684484 3.193949 H 0.746586 3.511041 2.674236 H 1.563030 4.386511 1.369262 H 2.748876 4.762094 1.232301 H 0.947166 4.343285 0.937162 H 0.137062 5.696076 0.600323 H 0.319972 4.789420 2.096325 H 5.517189 2.737250 0.291850 H 5.104259 3.805704 1.065048 H 5.203383 4.451445 0.573481 N 2.243237 3.070815 1.922123 O 1.929708 4.018589 1.191274 C 6.354621 2.287321 1.111230 H 6.415605 3.293547 1.528128 C 7.672749 1.563150 1.005752 H 8.093324 1.379185 2.001409 H 8.411189 2.162751 0.458042 O 7.541302 0.256941 0.425869 C 7.482962 0.071936 0.920019 O 7.111327 1.001112 1.339263 C 7.922967 1.206497 1.825027 H 8.969044 1.475874 1.639807 H 7.311064 2.100226 1.665519 H 7.817 582 0.873545 2.857706 C 1.632946 2.875956 0.028034 C 1.392503 1.834440 1.119106 C 3.829047 2.409619 0.872725 C 3.108258 2.707015 0.478799 H 1.592074 3.853934 0.471875 H 3.476412 3.659578 0.8 83960 C 2.829779 1.502965 1.641769

PAGE 174

167 H 3.072431 0.450448 1.443000 H 2.923016 1.640843 2.724691 C 0.660164 0.536875 0.757727 C 5.178123 1.761997 0.759959 H 0.809500 2.328247 1.896553 H 3.927836 3.364314 1.406571 H 1.235399 0.068395 0.057412 H 5.169982 0.743418 0.375118 C 3.338307 1.636328 1.552638 H 2.743183 1.848244 2.447025 H 4.390041 1.607666 1.859035 H 3.072089 0.633151 1.204307 C 0.580373 2.923663 1.135703 H 0.395217 3.165407 0.703022 H 0.824273 3.701968 1.870809 H 0.495297 1.973878 1.676275 C 0.324900 0.359295 2.066978 C 1.194256 0.600312 2.357356 C 1.637221 2.0 24770 2.623794 H 0.931360 2.735492 2.204710 H 1.706404 2.214045 3.703562 O 2.887799 2.378269 1.993355 C 4.093501 1.879211 2.380942 O 5.054074 2.122032 1.684079 C 4.180383 1.046095 3.643461 H 3.580858 1.450860 4.464288 H 3.837840 0.023316 3.444964 H 5.228126 1.003585 3.943719 H 0.832282 1.317714 1.943790 H 0.733848 0.201534 2.910377 H 1.558493 0.098471 3.111340 TS 26 E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1530058900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2705943700 a.u Ru 1.281311 0.650332 0.529838 O 0.938386 2.146963 1.169193 O 0.667596 2.744347 0.897991 N 3.497974 0.99020 2 0.367194 N 1.740900 2.300402 0.548191 C 2.149671 1.043288 0.187272 C 4.068331 2.210623 0.948043 C 4.144103 0.324472 0.487164 C 4.115607 0.804321 1.964239 C 4.736038 2.210391 2.083511 C 6. 188524 2.183022 1.570626 C 6.196784 1.730041 0.096267 C 5.614741 0.300106 0.007822 C 5.347616 2.711047 0.743795 C 3.880222 2.717500 0.231084 C 3.337848 1.279337 0.409104 C 3.902917 3.192904 1.239404 C 0.434666 2.731557 0.958382 C 0.066511 2.276820 2.200984 C 1.306771 2.748895 2.636777 C 0.723291 1.322471 3.066334 C 2.883819 3.184781 0.880150 C 0.263442 3.705256 0.220468 C 2.054545 3.669975 1.891900 C 1.508000 4.141147 0.697943 C 0.304807 4.327284 1.033759 C 3.408889 4.135393 2.373586 H 3.592115 1.005326 1.442716 H 4.916202 2.561365 0.355308 H 4.406989 2.032369 1.976994 H 3.078095 0.824954 2.315710 H 4.669539 0.099385 2.600385 H 4.721471 2.520788 3.136804 H 6.798898 1.500295 2.179312 H 6.638324 3.181074 1.660912 H 7.227994 1.718058 0.281469 H 5.65 8184 0.073714 1.023694 H 6.220871 0.380618 0.623874 H 5.377028 2.424602 1.804665 H 5.777422 3.720564 0.675181 H 3.290915 3.414445 0.838369 H 2.893903 3.267408 1.649267 H 4.347991 4.196715 1. 289004 H 1.693225 2.398572 3.591766 H 0.843026 0.342885 2.592260 H 0.221720 1.170266 4.026520 H 1.730335 1.705323 3.271535 H 2.697178 3.701684 1.826403 H 3.021058 3.924937 0.087110 H 2.056317 4.881082 0.118280 H 1.011393 3.669642 1.541951 H 0.839991 5.256545 0.793833 H 0.496202 4.596075 1.731481 H 4.178800 3.375796 2.184955 H 3.722069 5.052967 1.865588 H 3.405121 4.328184 3.452484 N 0.639265 3.086674 0.344283 O 0.351338 4.212975 0.707997 C 6.651591 2.125786 1.403063 H 6.430782 3.189738 1.505259 C 8.001069 1.718410 1.933225 H 8.029334 1.826688 3.024551 H 8.7870 14 2.372806 1.535073 O 8.315785 0.340909 1.700763 C 8.874374 0.084803 0.530431 O 9.018023 1.271700 0.363849 C 9.308606 0.958214 0.483187 H 10.131833 1.567450 0.091987 H 8.486310 1.630772 0.74 6726 H 9.653939 0.433235 1.374089 C 2.573594 1.786952 1.228244 C 1.973599 1.321616 0.163801 C 4.392706 1.726841 0.373070

PAGE 175

168 C 4.109510 1.527501 1.143427 H 2.451984 2.877212 1.249541 H 4.642345 2.294695 1.721052 C 3.223610 0.966015 1.028285 H 3.422340 0.112984 0.998450 H 3.095246 1.239025 2.081825 C 0.934738 0.198259 0.161361 C 5.744396 1.302697 0.869087 H 1.522026 2.200157 0.629943 H 4.265286 2.798350 0.585753 H 0.899388 0.420493 0.728395 H 5.980154 0.241180 0.803840 C 4.552797 0.157110 1.680975 H 4.326962 0.070371 2.748502 H 5.633391 0.018829 1.565398 H 4.052941 0.67 6709 1.173406 C 1.911787 1.261524 2.504830 H 0.862289 1.562319 2.545335 H 2.415171 1.682089 3.384664 H 1.961892 0.171308 2.590151 C 0.614206 0.475451 1.376563 C 1.117337 0.108967 2.338642 C 1.491963 1.001271 3.285673 H 0.600968 1.450078 3.745574 H 2.068133 0.548836 4.100893 O 2.209678 2.094604 2.702774 C 3.556796 2.248389 2.802395 O 4.071891 3.161594 2.197641 C 4.340291 1.299217 3.687541 H 4.008467 1.356640 4.730609 H 4.236537 0.261253 3.355425 H 5.389655 1.589891 3.634930 H 0.399924 1.536849 1.336491 H 1.145416 0.150091 2.269379 H 0.734226 0.942054 2.954476 TS 27 E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1442119400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2696942500 a.u Ru 1.334571 0.455109 0.670050 O 3.230494 2.221192 2.704349 O 1.275208 2.361293 1.669505 N 2.559536 1.273379 1.314956 N 0.810999 2.424919 0.664032 C 1.481686 1.240004 0.499865 C 2.649916 2.476572 2.146480 C 3.280742 0.025695 1.590184 C 2.582430 0.735437 2.750359 C 3.273478 2.090079 2.993691 C 4.754003 1.847634 3.350071 C 5.444667 1.101059 2.189978 C 4.755089 0.267324 1.981460 C 5.338997 1.955300 0.908275 C 3.848602 2.185512 0.540959 C 3.212431 0.798169 0.286436 C 3.173 877 2.933608 1.707534 C 0.563710 2.719808 0.373638 C 1.560293 2.196695 1.229518 C 2.900844 2.499638 0.971834 C 1.195838 1.366056 2.439880 C 1.567767 3.368502 1.520645 C 0.911717 3.613179 0.657620 C 3.280660 3.333760 0.087439 C 2.269006 3.885477 0.877160 C 0.126630 4.312976 1.504092 C 4.734516 3.666107 0.333470 H 3.876667 0.296056 0.426852 H 3.642090 2.924941 2.067643 H 2.4471 23 2.239086 3.200260 H 1.526631 0.892798 2.488595 H 2.600861 0.127648 3.666649 H 2.773633 2.608895 3.822990 H 4.830739 1.262956 4.278208 H 5.257750 2.806228 3.533751 H 6.500953 0.932020 2.43 7927 H 5.256206 0.843742 1.194244 H 4.826414 0.856054 2.908369 H 5.855666 1.459584 0.075385 H 5.842510 2.919932 1.065646 H 3.801548 2.787645 0.368733 H 2.123386 3.142015 1.474972 H 3.662521 3.906154 1.859291 H 3.671940 2.087481 1.619198 H 0.669288 0.442502 2.176065 H 2.092800 1.092445 3.002303 H 0.534568 1.920285 3.117551 H 0.905797 3.830809 2.258524 H 2.010330 4.155678 0.900613 H 2.538238 4.559943 1.688337 H 1.108795 3.846202 1.422881 H 0.231376 5.361170 1.192745 H 0.173131 4.329848 2.558972 H 5.405232 2.909490 0.085472 H 4.943669 3.759428 1.405114 H 4.997242 4.62 7033 0.129696 N 2.239727 2.905128 2.387150 O 2.088618 4.079721 2.717959 C 6.608985 2.142294 0.850003 H 6.779245 3.171257 1.169783 C 7.858213 1.316475 0.674592 H 8.359127 1.161900 1.637522 H 8.579590 1.825766 0.022824 O 7.583578 0.009112 0.197568 C 7.383181 0.269268 1.122136 O 6.908135 1.338171 1.433731 C 7.800330 0.777410 2.137208 H 8.875450 0.980888 2.074837 H 7.268368 1.720508 1.975547

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169 H 7.567481 0.393879 3.130730 C 1.842013 2.931524 0.080651 C 1.644517 1.931361 1.260567 C 4.086872 2.438304 0.841440 C 3.271011 2.681974 0.468487 H 1.880104 3.923840 0.552522 H 3.63 7090 3.596422 0.954731 C 3.104149 1.680998 1.783089 H 3.332210 0.609276 1.775213 H 3.222225 2.013048 2.820096 C 0.993595 0.589785 0.944001 C 5.370245 1.679808 0.663063 H 1.039072 2.412495 2.031288 H 4.308156 3.422774 1.274042 H 1.285027 0.110072 0.012304 H 5.254839 0.637280 0.370275 C 3.385273 1.549162 1.499135 H 2.723318 1.731444 2.352286 H 4.407090 1.481607 1.888794 H 3.1340 18 0.567478 1.083406 C 0.716544 2.986477 0.950840 H 0.215051 3.281204 0.460861 H 0.935619 3.719413 1.737900 H 0.554011 2.020386 1.445608 C 0.605615 0.263063 1.968816 C 1.810879 0.327033 2.27 5091 C 2.373030 1.642833 2.736601 H 1.572953 2.235110 3.202197 H 3.110131 1.445348 3.523534 O 2.929769 2.487592 1.724880 C 4.252781 2.463993 1.395749 O 4.613568 3.144918 0.462952 C 5.195991 1.622341 2.231721 H 5.238975 1.989945 3.263986 H 4.893653 0.570522 2.264461 H 6.190037 1.701030 1.790905 H 0.627442 1.337420 1.842726 H 0.610057 0.106704 2.992124 H 1.728134 0.351792 3.132096 TS 28 E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1443432400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution : 2343.2697230000 a.u Ru 1.433836 0.518687 0.677682 O 0.791757 2.385266 3.457883 O 1.574208 2.558216 1.399095 N 2.704663 1.226957 1.254335 N 0.967459 2.395662 0.592715 C 1.620186 1.198432 0.440258 C 2.798522 2.431654 2.083314 C 3.395044 0.032220 1.559718 C 2.679959 0.758197 2.731682 C 3.3358 34 2.128461 2.988519 C 4.822615 1.919396 3.340323 C 5.531481 1.205989 2.170278 C 4.875900 0.177560 1.944154 C 5.405283 2.076279 0.899817 C 3.909953 2.273848 0.537573 C 3.306651 0.877244 0.27 5418 C 3.213272 2.986013 1.713214 C 0.415247 2.701682 0.346053 C 1.381840 2.219815 1.259748 C 2.726780 2.542505 1.056101 C 0.981179 1.405240 2.469383 C 1.753228 3.340350 1.423398 C 0.795660 3.572292 0.692862 C 3.141123 3.353942 0.007771 C 2.157277 3.862086 0.858775 C 0.210389 4.234456 1.605845 C 4.598204 3.710004 0.194515 H 3.975624 0.390982 0.448042 H 3.800837 2.861185 2.031387 H 2.562103 2.203142 3.132455 H 1.619676 0.890307 2.475528 H 2.718716 0.140745 3.640681 H 2.824304 2.623910 3.824859 H 4.915882 1.324849 4.260582 H 5.302173 2.887968 3.535805 H 6.591663 1.05 9955 2.416070 H 5.389616 0.728216 1.145735 H 4.966543 0.778321 2.861412 H 5.936987 1.602638 0.062504 H 5.886766 3.049671 1.071721 H 3.819532 2.886695 0.363983 H 2.159189 3.164209 1.474218 H 3.671829 3.970776 1.878987 H 3.473014 2.163754 1.751085 H 0.508626 0.454968 2.198050 H 1.855038 1.179997 3.086929 H 0.261524 1.946235 3.096130 H 1.104324 3.849674 2.141013 H 2.230565 4.085708 0.778655 H 2.451307 4.518110 1.676415 H 1.196859 3.775982 1.536314 H 0.317895 5.296674 1.347994 H 0.124667 4.199642 2.649738 H 5.265571 2.975173 0.266894 H 4.853958 3.788370 1.257083 H 4.82 1676 4.683888 0.262137 N 1.180237 3.113655 2.517273 O 1.216891 4.339839 2.585306 C 6.607880 1.943788 0.763984 H 6.774058 2.956671 1.133331 C 7.859805 1.129647 0.557492 H 8.366810 0.951423 1. 513114 H 8.575193 1.660197 0.084067 O 7.588083 0.183347 0.046135 C 7.378611 0.408632 1.278646

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170 O 6.898239 1.467541 1.614776 C 7.792366 0.663622 2.268183 H 8.867093 0.868048 2.202742 H 7.258450 1.601129 2.081859 H 7.558070 0.304792 3.270563 C 1.851828 2.823601 0.047999 C 1.642937 1.817780 1.227600 C 4.086078 2.233498 0.763581 C 3.263867 2.535620 0.527484 H 1.928210 3.810484 0.52568 2 H 3.655043 3.445423 1.002805 C 3.103220 1.427444 1.654740 H 3.266320 0.354148 1.500199 H 3.276917 1.614839 2.719516 C 0.870992 0.531463 0.958351 C 5.371080 1.487987 0.549437 H 1.155323 2.327827 2.059511 H 4.301524 3.196151 1.246177 H 1.151347 0.010374 0.057386 H 5.258736 0.460604 0.206439 C 3.318948 1.415120 1.576102 H 2.658963 1.638757 2.420850 H 4.333342 1.305373 1.975552 H 3.024630 0.441103 1.170103 C 0.719241 2.925668 0.973572 H 0.194398 3.275778 0.486264 H 0.973707 3.635384 1.771256 H 0.503469 1.962606 1.454290 C 0.426212 0.254540 2.022422 C 1.923242 0.20 5775 2.310905 C 2.478480 1.506895 2.820970 H 1.689116 2.057110 3.351635 H 3.250444 1.281055 3.565998 O 2.979897 2.417693 1.835462 C 4.294638 2.504567 1.496311 O 4.598388 3.249794 0.592570 C 5.307505 1.695586 2.282327 H 5.325629 1.998299 3.335804 H 5.089977 0.623241 2.244785 H 6.289656 1.879771 1.846541 H 0.399475 1.332832 1.934158 H 0.452170 0.163571 3.024980 H 1.839258 0.524435 3.127714 11E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1619093200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2921131400 a.u Ru 1.561922 0.019636 0.550420 O 3.673600 0.183229 2.857919 O 1.755734 0.861414 2.518848 N 2.676812 0.249930 2.108701 N 0.807043 1.382050 2.280265 C 1.555786 0.609086 1.427379 C 2.703979 0.682009 3.509393 C 3.517283 0.837826 1.599701 C 3.064545 2.190964 2.212234 C 3.890 379 3.346106 1.615926 C 5.385520 3.113807 1.913384 C 5.833198 1.775892 1.288681 C 5.017284 0.621676 1.914654 C 5.598855 1.821725 0.236076 C 4.090998 2.042877 0.532425 C 3.326909 0.856468 0.0 77350 C 3.655463 3.382681 0.095078 C 0.593580 1.691632 2.191004 C 1.530253 0.657796 2.410637 C 2.894330 0.956518 2.329284 C 1.079185 0.731563 2.802540 C 1.466399 1.587135 3.591798 C 1.025789 3.024351 2.049189 C 3.353857 2.256458 2.083136 C 2.401917 3.274092 1.969862 C 0.069612 4.195948 2.085242 C 4.832585 2.559512 2.006874 H 3.757907 0.083006 0.342964 H 3.630070 1.217890 3.737332 H 2.636109 0.179595 4.185048 H 1.997265 2.337100 2.000468 H 3.183849 2.170087 3.304348 H 3.564786 4.291919 2.068778 H 5.560536 3.105255 2.998704 H 5.981893 3.937848 1.499980 H 6.898202 1.6 09261 1.495356 H 5.340942 0.345530 1.507988 H 5.185393 0.595024 3.001426 H 5.937324 0.891481 0.709245 H 6.186635 2.637999 0.678084 H 3.941553 2.076304 1.612044 H 2.598679 3.578620 0.116772 H 4.230077 4.202545 0.356597 H 3.621789 0.162042 2.479664 H 0.469925 1.209429 2.029447 H 1.940922 1.373627 3.001036 H 0.471577 0.704389 3.716302 H 0.787135 1.310547 4.404090 H 1.732356 2.642244 3.720674 H 2.737442 4.301080 1.835792 H 0.955624 3.910164 1.843871 H 0.057701 4.642303 3.088936 H 0.379908 4.988460 1.395709 H 5.428834 1.654361 1.857646 H 5.051143 3.255712 1.188869 H 5.1 80559 3.035443 2.933576 N 2.813517 0.614730 3.272579 O 2.879899 1.201906 4.348378 C 6.038806 1.670550 2.102261 H 6.109073 2.232329 3.034671 C 7.357911 1.201395 1.542745

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171 H 7.825766 0.472038 2 .214241 H 8.064156 2.035447 1.441718 O 7.212700 0.500024 0.298624 C 7.088424 1.156529 0.884737 O 6.708003 0.534867 1.851967 C 7.468052 2.623505 0.942188 H 8.519378 2.769710 0.669279 H 6.855653 3.218070 0.256532 H 7.312740 2.971610 1.963492 C 1.261279 2.630508 1.643557 C 1.089034 1.101542 1.929197 C 3.503225 1.821282 2.060444 C 2.722576 2.834861 1.165557 H 1.213031 3.105039 2.6343 49 H 3.046053 3.855893 1.410419 C 2.551410 0.597723 2.179364 H 2.828311 0.150063 1.424741 H 2.662426 0.107963 3.152893 C 0.425514 0.229142 0.853133 C 4.852807 1.414551 1.544400 H 0.493227 1.001348 2.837386 H 3.617757 2.281516 3.050762 H 1.027684 0.186499 0.054740 H 4.837416 0.825676 0.628465 C 2.944756 2.637844 0.338978 H 2.308105 3.314331 0.918859 H 3.983761 2.852504 0.613099 H 2.726615 1.615051 0.662033 C 0.168731 3.286902 0.802167 H 0.799436 3.157067 1.294408 H 0.351536 4.363467 0.688971 H 0.096814 2.853691 0.202100 C 0.177700 1.271771 1.390853 C 1.313344 1.74 1492 1.465014 C 1.691639 3.087860 0.867116 H 2.603470 2.999519 0.270925 H 0.902067 3.483193 0.227051 O 2.054614 4.043764 1.885518 C 1.167789 4.870223 2.503404 O 1.573201 5.602010 3.373590 C 0.283219 4.855690 2.053900 H 0.378981 5.154039 1.003945 H 0.734191 3.864733 2.159933 H 0.828112 5.567683 2.674202 H 0.739776 1.947758 0.744936 H 0.570038 1.278942 2.411200 H 1.733269 1.660040 2.469030 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1684660100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2933977200 a.u Ru 1.378032 0.394285 0.570980 O 1.280716 3.558263 0.479567 O 1.548997 2.001566 2.009188 N 2.720630 1.205495 1.432298 N 0.945638 2.413178 1.017459 C 1.571429 1.223981 0.721411 C 3.002402 2.432817 2.179242 C 3.585845 0.028251 1.447716 C 3.311723 0.811252 2.724161 C 4.15 9467 2.097029 2.703895 C 5.654842 1.724777 2.638445 C 5.924150 0.901220 1.361972 C 5.090219 0.399155 1.400014 C 5.535302 1.736144 0.125105 C 4.026663 2.104162 0.187270 C 3.236624 0.788745 0. 198487 C 3.766923 2.926087 1.466410 C 0.430415 2.770407 0.806073 C 1.433409 2.154416 1.589058 C 2.768634 2.500745 1.365541 C 1.080376 1.205919 2.712549 C 1.679569 3.196201 2.038904 C 0.760615 3.833302 0.057181 C 3.137604 3.472270 0.425966 C 2.115280 4.139965 0.252419 C 0.288796 4.718298 0.696559 C 4.590280 3.830007 0.210244 H 3.539890 0.186359 0.696177 H 3.841708 2.969350 1.72235 9 H 3.258703 2.216257 3.221365 H 2.243377 1.060177 2.762595 H 3.542921 0.211773 3.616561 H 3.960265 2.673120 3.617167 H 5.945036 1.150056 3.529716 H 6.267567 2.636175 2.633053 H 6.988007 0. 635952 1.309125 H 5.288916 1.015175 0.513955 H 5.369144 0.988981 2.285392 H 5.751212 1.175523 0.794145 H 6.135907 2.655537 0.089531 H 3.767968 2.694033 0.694327 H 2.713578 3.218514 1.511986 H 4.356260 3.852248 1.431203 H 3.543575 2.012055 1.951803 H 0.355204 0.446989 2.411703 H 1.972105 0.697310 3.086710 H 0.641831 1.754223 3.557488 H 1.106764 3.219468 2.974171 H 1.820303 4.227432 1.703171 H 2.372069 4.940033 0.944483 H 1.278356 4.257509 0.716645 H 0.373494 5.658149 0.133832 H 0.011688 4.991468 1.720893 H 5.250769 2.963321 0.321283 H 4.750868 4.256579 0.785402 H 4.920004 4.579994 0.941951 N 1.503160 3.269533 1.669909

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172 O 1.680127 4.101423 2.556786 C 6.398015 2.273451 1.147399 H 6.423533 3.307674 1.493464 C 7.717894 1.547927 1.218105 H 8.055517 1.466 202 2.258066 H 8.500131 2.095006 0.676004 O 7.630756 0.190463 0.762360 C 7.693313 0.133344 0.557964 O 7.368025 1.249090 0.893874 C 8.203764 0.911207 1.532359 H 9.232359 1.204264 1.292763 H 7.582518 1.812402 1.509995 H 8.180654 0.477983 2.532467 C 1.790634 2.760339 0.468836 C 1.446873 1.859500 0.777719 C 3.902493 2.362840 0.672826 C 3.309036 2.569418 0.753891 H 1.680627 3.791131 0.108558 H 3.715228 3.493508 1.187313 C 2.841921 1.487280 1.380346 H 3.065389 0.430315 1.182086 H 2.876432 1.613305 2.467866 C 0.634222 0.585231 0.530961 C 5.257797 1.719354 0.728111 H 0.906 709 2.473295 1.499557 H 3.942470 3.345973 1.161011 H 1.121206 0.042533 0.215517 H 5.283124 0.675639 0.418434 C 3.644639 1.428560 1.725456 H 3.174411 1.596438 2.699573 H 4.725486 1.362200 1.8 92480 H 3.309233 0.452972 1.356051 C 0.884336 2.639479 1.696913 H 0.147300 2.870177 1.424837 H 1.198714 3.350133 2.472587 H 0.909557 1.639774 2.139243 C 0.421930 0.279019 1.884825 C 1.060655 0.582720 2.279851 C 1.410192 2.033980 2.533767 H 0.732443 2.690787 1.997446 H 1.339699 2.275323 3.602418 O 2.717985 2.396732 2.036988 C 3.871402 2.100425 2.692708 O 4.918039 2.245574 2.102049 C 3.789263 1.633563 4.133279 H 3.253835 2.356473 4.758627 H 3.270145 0.672639 4.211443 H 4.806883 1.518877 4.507313 H 0.958232 1.220590 1.746574 H 0.862474 0.312586 2.689125 H 1.391081 0.072676 3.090612 11 E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2344.1684444500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2343.2910637000 a.u Ru 1.392249 0.425035 0.430290 O 0.981021 2.597132 3.110709 O 1.732777 2.486151 1.034583 N 2.556268 1.549742 1.308733 N 0.785659 2.598197 0.539800 C 1.463942 1.395491 0.528073 C 2.746469 2.899176 1.840813 C 3.366234 0.394825 1.700493 C 2.924799 0.087593 3.107824 C 3.695489 1.362875 3.496369 C 5.208234 1.060574 3.500190 C 5.645375 0.592783 2.096622 C 4.884665 0.700431 1.719665 C 5.334606 1.705643 1.073313 C 3.809542 2.000644 1.057779 C 3.103183 0.6 98701 0.660019 C 3.377298 2.462612 2.464399 C 0.623765 2.803953 0.312936 C 1.551853 2.277962 1.243925 C 2.914053 2.519844 1.048994 C 1.097684 1.496773 2.456530 C 1.439651 3.592987 1.427044 C 1.065165 3.648024 0.722907 C 3.387486 3.295717 0.017558 C 2.443284 3.857190 0.877886 C 0.123236 4.382154 1.652584 C 4.863875 3.569155 0.187622 H 3.540495 0.348134 0.310585 H 3.627175 3.365883 1.385390 H 2.891827 2.882998 2.926213 H 1.844763 0.282847 3.093009 H 3.105613 0.705955 3.846955 H 3.378669 1.684767 4.497347 H 5.438112 0.288251 4.248214 H 5.770172 1.959517 3.786836 H 6.7 22123 0.380178 2.095835 H 5.199313 1.061960 0.732618 H 5.110282 1.489082 2.452793 H 5.670587 1.405875 0.072284 H 5.884981 2.619444 1.337461 H 3.585313 2.775028 0.321808 H 2.304796 2.693789 2 .475658 H 3.906046 3.389498 2.724785 H 3.628809 2.105839 1.756494 H 0.566776 0.580296 2.181560 H 1.954823 1.217710 3.075031 H 0.416547 2.084254 3.084607 H 0.791060 3.812561 2.283091 H 1.611770 4.530246 0.889493 H 2.781966 4.497829 1.690312 H 0.919716 4.297594 1.341588 H 0.379837 5.447481 1.684718 H 0.198436 4.009301 2.681629

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173 H 5.484546 2.744699 0.177901 H 5.114619 3.749622 1.2384 42 H 5.158534 4.466450 0.373726 N 1.578978 3.143011 2.158614 O 2.033914 4.283282 2.210373 C 6.335627 2.230985 0.942867 H 6.393738 3.260881 1.297766 C 7.649412 1.491994 0.921374 H 8.030374 1 .350478 1.939674 H 8.413737 2.059871 0.375473 O 7.527696 0.161460 0.397112 C 7.514663 0.083513 0.940279 O 7.155628 1.174234 1.323296 C 7.984132 1.010101 1.880130 H 9.023397 1.289924 1.673491 H 7.366208 1.908268 1.779836 H 7.912329 0.631274 2.899790 C 1.648006 2.794307 0.339510 C 1.372852 1.869363 0.898605 C 3.822022 2.364274 0.628110 C 3.123767 2.551002 0.754640 H 1.627271 3.816277 0.065274 H 3.518948 3.453197 1.241509 C 2.797763 1.545482 1.458865 H 3.014254 0.474793 1.346677 H 2.884573 1.767828 2.527767 C 0.599573 0.568640 0.661763 C 5.163878 1.694354 0.592206 H 0.819837 2.446362 1.639749 H 3.926769 3.361260 1.076772 H 1.181629 0.139320 0.071212 H 5.154059 0.653729 0.271719 C 3.338378 1.380483 1.723463 H 2.771916 1.531829 2.648367 H 4.394818 1.28 9808 2.000054 H 3.029528 0.420550 1.296290 C 0.614091 2.759373 1.465539 H 0.371173 3.036070 1.078242 H 0.879233 3.469460 2.259835 H 0.528988 1.767221 1.923065 C 0.163301 0.153550 2.053548 C 1.374978 0.255733 2.303531 C 1.949908 1.604429 2.675305 H 1.417418 2.409670 2.179034 H 1.906805 1.775211 3.759584 O 3.310641 1.749295 2.206277 C 4.382170 1.204907 2.842912 O 5.437808 1.169977 2.251765 C 4.208683 0.711423 4.266403 H 3.835306 1.508129 4.919575 H 3.502794 0.123690 4.320355 H 5.181989 0.377532 4.626491 H 0.607520 1.150527 2.048660 H 0.575412 0.473995 2.845595 H 1.708978 0.545591 2.964433 TS8* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0479887700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1822546300 a.u Ru 1.069935 0.506506 0.119671 O 0.242830 1.419784 1.830243 O 0.949311 1.436225 0.019089 N 3.884323 1.184295 0.069680 N 3.862246 0.985849 0.226258 C 3.057774 0.112809 0.062495 C 5.295989 0.878596 0.180715 C 3.334058 2.541391 0.029885 C 3.361295 3.021022 1.505586 C 2.730236 4.422476 1.621205 C 3.502033 5.414616 0.730008 C 3.441594 4.935315 0.734691 C 4.123059 3.550986 0.836585 C 1.964750 4.844795 1.181773 C 1.201630 3.823775 0.291812 C 1.890 944 2.452768 0.497095 C 1.261739 4.340109 1.163907 C 3.517453 2.311071 0.648003 C 3.256301 2.543394 2.015813 C 2.974735 3.848487 2.427685 C 3.321947 1.424475 3.031588 C 5.299892 0.652604 0.120187 C 3.570202 3.378531 0.267590 C 2.970696 4.925256 1.532033 C 3.283000 4.669499 0.194905 C 3.945940 3.173282 1.717618 C 2.632721 6.321053 2.001911 H 1.974322 2.331752 1.587043 H 5.9407 24 1.330340 0.577663 H 5.608268 1.256073 1.163852 H 2.806633 2.306720 2.125294 H 4.397328 3.049085 1.872556 H 2.775597 4.751607 2.667685 H 4.548246 5.493601 1.059238 H 3.063107 6.417507 0.81 7082 H 3.978967 5.643955 1.378767 H 4.141358 3.202142 1.878168 H 5.167752 3.634835 0.501064 H 1.906680 4.546136 2.237729 H 1.496880 5.836584 1.104878 H 0.158306 3.767915 0.622595 H 0.703516 3.692614 1.842400 H 0.799043 5.335688 1.213614 H 2.767197 4.032297 3.479831 H 2.626304 0.608984 2.806665 H 3.089337 1.799249 4.032661 H 4.325186 0.980808 3.069745 H 5.861116 1.115819 0.936668 H 5.704543 1.026934 0.828555

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174 H 3.308792 5.495287 0.513147 H 5.024622 3.314882 1.868825 H 3.434708 3.895881 2.361543 H 3.697059 2.168092 2.067938 H 1.546031 6.471034 2.046692 H 3.039654 7.08 1008 1.327230 H 3.026375 6.511586 3.006299 C 1.056678 0.264519 1.839394 H 1.838439 0.900537 2.273441 N 0.861947 1.742376 1.270289 O 1.772438 2.294419 1.866354 C 1.440127 3.035367 1.532276 C 1.300542 1.500357 1.256725 C 0.974333 2.419668 0.795799 C 1.194596 3.668673 0.127040 H 2.446052 3.263080 1.895934 H 2.070305 4.225555 0.215878 C 1.945775 1.414995 0.151811 H 1.906986 0.417659 0.585292 C 0.182851 1.316587 0.934532 C 0.376007 1.886362 0.342650 H 1.712182 0.859225 2.037598 H 1.095876 2.609331 1.862075 H 0.905988 1.436223 1.731560 C 0.014804 0.055553 2.871657 H 0.393752 0.924046 3.436888 O 0.141567 1.070425 3.760525 C 0.970848 1.027328 4.845673 O 1.047267 2.006144 5.546982 C 1.746698 0.251184 5.095450 H 1.077142 1.107517 5.233674 H 2.409358 0.485899 4.254867 H 2.344925 0.113747 5.996310 H 1.278512 2.415008 0.613194 H 0.944542 0.340448 2.430281 O 3.270341 1.936271 0.243673 C 4.346849 1.154029 0.061420 C 5.598194 1.758311 0.149499 C 4.27 8581 0.157677 0.545386 C 6.764619 1.059056 0.120089 H 5.626272 2.773704 0.531835 C 5.460715 0.850749 0.814151 H 3.333297 0.655556 0.717934 C 6.703519 0.255069 0.605087 H 7.728365 1.528336 0. 053095 H 5.401751 1.866919 1.188653 C 7.976341 0.977946 0.930221 F 8.547591 0.514129 2.069924 F 7.786545 2.305036 1.098865 F 8.904382 0.823044 0.045998 H 0.722566 3.373997 2.285759 H 0.332335 4.342386 0.103542 TS9* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0538613300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1989470500 a.u Ru 1.001025 0.664351 0.291686 O 2.520642 2.067257 1.298570 O 0.893743 0.605503 1.370591 N 3.256350 2.180304 0.649271 N 3.812886 0.125425 1.155848 C 2.844710 0.891136 0.561043 C 4.436195 2.367447 1.497572 C 2.339096 3.252279 0.265636 C 1.502801 3.729827 1.48403 7 C 0.490292 4.803673 1.039884 C 1.254323 6.002051 0.439942 C 2.084059 5.530686 0.772209 C 3.102798 4.465533 0.316315 C 1.146089 4.918390 1.827976 C 0.375382 3.711102 1.227085 C 1.404693 2. 647602 0.804058 C 0.450232 4.194749 0.016643 C 4.020051 1.293778 1.067275 C 3.815579 2.087303 2.212489 C 4.048120 3.465242 2.119130 C 3.387922 1.495246 3.536391 C 4.977517 0.937857 1.576838 C 4.535236 1.857199 0.121014 C 4.494551 4.063313 0.938373 C 4.744395 3.237855 0.164228 C 4.911436 1.010812 1.318644 C 4.698386 5.556766 0.843570 H 2.012675 2.356678 1.687773 H 5.147880 3.06668 0 1.052108 H 4.144534 2.753916 2.483778 H 0.979736 2.867958 1.920014 H 2.171036 4.134449 2.257499 H 0.089217 5.133511 1.911908 H 1.910360 6.454542 1.197401 H 0.545127 6.779594 0.127189 H 2. 627729 6.381607 1.202776 H 3.724308 4.138054 1.160668 H 3.775349 4.895600 0.440101 H 1.719983 4.597491 2.708146 H 0.425998 5.671548 2.174750 H 0.280048 3.323625 2.005115 H 1.021453 3.360992 0.406378 H 1.184019 4.941518 0.345933 H 3.873418 4.085059 2.996082 H 2.836990 0.560332 3.411172 H 2.757691 2.195681 4.093652 H 4.260651 1.278955 4.168033 H 5.303859 0.652737 2.580476 H 5.81393 2 0.775144 0.884989 H 5.114793 3.681196 1.085904 H 5.921280 0.594630 1.200778 H 4.917875 1.615622 2.230345

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175 H 4.229737 0.170759 1.475330 H 3.912722 6.021678 0.234779 H 5.656970 5.800216 0.371302 H 4.677054 6.028289 1.830988 C 1.281626 1.161560 1.127714 H 2.324444 1.440252 1.260313 N 1.648131 1.499850 1.967051 O 1.468589 1.692806 3.173504 C 0.949421 1.896618 2.718184 C 1.0998 65 0.742742 1.681466 C 0.481743 2.516346 0.396242 C 0.491372 3.103912 1.835217 H 1.910465 2.102600 3.197104 H 1.206892 3.927202 1.897491 C 1.654500 1.524584 0.468425 H 1.779480 0.913599 0.42 0254 C 0.335870 0.380194 1.270787 C 0.779447 1.614337 0.285148 H 1.699373 0.101795 2.028757 H 0.542064 3.268578 0.393006 H 0.988684 0.311724 2.142757 C 0.511268 1.576560 2.368528 H 0.739910 0.896974 3.196195 O 0.983773 2.910355 2.684322 C 0.510168 3.601943 3.759801 O 0.975780 4.692167 3.992216 C 0.582587 2.959067 4.591353 H 0.267906 1.991174 4.996361 H 1.482163 2.779950 3.991735 H 0.826321 3.633718 5.412278 H 1.638470 2.082010 0.761129 H 0.566705 1.578273 2.220205 O 2.852273 2.255284 0.745893 C 4.059936 1.619197 0.709394 C 5.164903 2.415774 1.052905 C 4.249685 0.27 8389 0.350267 C 6.444086 1.878690 1.039978 H 4.994078 3.454098 1.319227 C 5.542114 0.247800 0.337368 H 3.425177 0.363174 0.061546 C 6.642110 0.538775 0.681226 H 7.294588 2.501249 1.299226 H 5.684877 1.282450 0.043429 C 8.018666 0.053300 0.727203 F 8.341398 0.499775 1.968345 F 8.149516 1.108743 0.107575 F 8.970229 0.850295 0.389842 H 0.231994 1.645214 3.506694 H 0.491918 3.494021 2.118799 TS10* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0654964300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2040874700 a.u Ru 0.725232 0.594071 0.321941 O 0.875147 0.540549 2.694259 O 0.973693 0.073512 1.660943 N 2.273045 2.817220 0.676777 N 3.520689 1.068157 1.110949 C 2.343046 1.472523 0.539467 C 3.329482 3.380889 1.520199 C 1.055051 3.517530 0.257128 C 0.070418 3.691679 1.440154 C 1.2 46036 4.313707 0.934709 C 0.950139 5.699929 0.327915 C 0.040280 5.543214 0.844273 C 1.358395 4.920009 0.325017 C 0.595603 4.634707 1.918020 C 0.881070 3.232023 1.318653 C 0.467642 2.637102 0 .868639 C 1.859749 3.387939 0.136295 C 4.200471 0.177295 0.887217 C 4.350924 1.081560 1.954485 C 5.004647 2.296429 1.713713 C 3.841510 0.765112 3.342418 C 4.330987 2.218583 1.574414 C 4.772869 0.445215 0.375474 C 5.530287 2.620122 0.460301 C 5.427263 1.666336 0.560274 C 4.658766 0.530119 1.525685 C 6.157704 3.967266 0.194644 H 1.164414 2.710830 1.714959 H 3.756371 4.287137 1.082167 H 2.936491 3.633820 2.514458 H 0.121666 2.716995 1.900207 H 0.520976 4.336736 2.208580 H 1.941593 4.420610 1.777710 H 0.532524 6.367301 1.095232 H 1.879684 6.164554 0.027330 H 0.2617 20 6.528212 1.275579 H 2.088355 4.829413 1.140287 H 1.797625 5.578049 0.439738 H 0.071972 4.541267 2.784783 H 1.528274 5.090060 2.279854 H 1.338977 2.602664 2.088279 H 2.087093 2.406359 0.29 8072 H 2.810267 3.808773 0.492260 H 5.097169 3.011052 2.528549 H 4.549757 0.128409 3.890182 H 2.885718 0.233108 3.319058 H 3.714114 1.680295 3.928729 H 4.725497 2.036353 2.577573 H 5.180359 2.372597 0.896518 H 5.861320 1.884441 1.533962 H 4.951705 1.546381 1.238975 H 5.303912 0.221350 2.353690 H 3.631674 0.591892 1.905026 H 5.442111 4.623801 0.317224 H 7.040952 3.878103 0.447920

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176 H 6.459398 4.461168 1.123703 N 0.364716 0.243217 2.790867 O 0.941931 0.119485 3.855732 C 1.448990 1.436690 0.550109 H 2.531816 1.381654 0.611491 C 0.884919 2.343924 1.624509 H 1.136307 1.974700 2.618770 H 0.196150 2.462464 1.564686 O 1.420165 3.677589 1.419863 C 2.558689 4.108418 2.024249 O 3.095566 5.107125 1.600961 C 0.352210 2.497120 2.751312 C 0.252157 2.392559 1.206263 C 1.272674 0.429810 1.838128 C 1.096502 1.192115 3.177873 H 0.929155 3.383225 3.026783 H 2.069269 1.424071 3.620251 C 1.519441 1.595806 0.854065 H 1.567431 1.294724 0.190173 C 0.940664 1.50 0942 0.813412 C 0.070707 0.179901 1.436329 H 0.189126 3.365903 0.712902 H 2.068743 0.322237 1.857021 H 1.735499 1.470806 1.553044 H 0.656668 0.442277 2.326860 H 0.535632 0.597732 3.907151 H 0.636672 2.594439 3.212045 O 2.661351 2.385789 1.188307 C 3.909140 1.955591 0.841197 C 4.180044 0.835752 0.043242 C 4.969275 2.731114 1.338926 C 5.504849 0.505764 0.247247 H 3.382325 0.227588 0.366528 C 6.281412 2.391118 1.045176 H 4.736102 3.593183 1.955633 C 6.559286 1.270768 0.250488 H 5.712298 0.362144 0.864339 H 7.096160 2.989337 1.440885 C 7.980327 0.939970 0.097491 F 8.44 1595 1.688326 1.129299 F 8.817420 1.168980 0.943058 F 8.129582 0.354917 0.458315 C 3.072413 3.345322 3.232491 H 2.308631 3.275975 4.014855 H 3.374361 2.325398 2.973236 H 3.936435 3.884993 3. 621340 TS11* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0706436900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2023247100 a.u Ru 0.596556 0.652127 0.270437 O 1.399451 0.052009 2.330229 O 0.569505 0.652096 1 .732557 N 1.489161 3.328119 0.300709 N 3.128245 1.988030 0.891251 C 1.864016 2.026305 0.384301 C 2.437352 4.242356 0.940615 C 0.106383 3.625836 0.079920 C 0.778765 3.856062 1.171800 C 2.253352 4.012475 0.757236 C 2.388898 5.231674 0.175477 C 1.506004 5.019188 1.422571 C 0.024463 4.870481 0.990876 C 1.988446 3.748736 2.157845 C 1.837531 2.512319 1.228943 C 0.340827 2.393431 0.8971 17 C 2.702955 2.729452 0.028227 C 3.996642 0.842876 0.870775 C 4.221147 0.133932 2.064115 C 5.072533 0.977917 2.031843 C 3.566011 0.553160 3.360219 C 3.681504 3.344657 1.093806 C 4.653381 0 .479698 0.324696 C 5.710949 1.388408 0.857905 C 5.496588 0.635468 0.303852 C 4.461779 1.252629 1.610063 C 6.599814 2.609461 0.823812 H 0.205230 2.437202 1.857523 H 2.627976 5.124400 0.322344 H 2.057141 4.582309 1.913824 H 0.669022 3.016943 1.863499 H 0.437065 4.758514 1.699027 H 2.867164 4.163706 1.654939 H 2.090506 6.147558 0.353912 H 3.436266 5.364249 0.477842 H 1.592910 5.886099 2.090216 H 0.622942 4.754355 1.869933 H 0.297875 5.780259 0.462998 H 1.412033 3.596981 3.080004 H 3.039221 3.872560 2.454614 H 2.169747 1.614285 1.762719 H 2.623285 1.866063 0.700125 H 3.759880 2.812853 0.259254 H 5.235442 1.539936 2.948824 H 3.963883 1.509656 3.724182 H 2.484539 0.682706 3.245665 H 3.742244 0.191492 4.142255 H 4.150595 3.430147 2.077955 H 4.441875 3.563 072 0.333678 H 5.996781 0.930182 1.224002 H 4.648712 2.324671 1.478548 H 5.152841 0.891055 2.377265 H 3.445575 1.143141 2.001224 H 6.229637 3.344365 0.098513 H 7.622103 2.346746 0.524220 H 6.651332 3.093948 1.803718 N 0.355201 0.650260 2.625099 O 0.262105 1.271945 3.665853

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177 C 2.039468 2.489702 0.023473 H 2.980156 1.974531 0.160532 C 1.715136 3.568102 0.974113 H 1.301957 3.165915 1.905035 H 0.994542 4.288470 0.579238 O 2.911667 4.329374 1.233142 C 3.819233 3.938861 2.173534 O 4.931079 4.413659 2.125188 C 0.085593 2.561580 3.161555 C 0.043450 2.725225 1.627896 C 1.065609 0.594476 1.958975 C 0.618905 1.115184 3.372319 H 0.805372 3.290153 3.542937 H 1.459435 1.107983 4.072224 C 1.147652 1.887718 1.115633 H 1.118235 1.735417 0.038317 C 1.351988 2.158105 1.128234 C 0.143621 0.495141 1.425495 H 0.078700 3.766206 1.308520 H 2.064790 0.136928 2.026741 H 1.802456 1.396853 1.760845 H 0.106850 1.167452 2.263357 H 0.149219 0.458787 3.796238 H 0.86 6018 2.737620 3.673877 O 2.325859 2.636410 1.473620 C 3.546104 2.263301 0.996255 C 3.758971 1.314496 0.014039 C 4.645482 2.915114 1.580544 C 5.061556 1.031426 0.427341 H 2.930567 0.805173 0. 490856 C 5.935442 2.624180 1.162029 H 4.459213 3.643390 2.363345 C 6.153674 1.674579 0.154767 H 5.222859 0.295623 1.208301 H 6.779663 3.125512 1.624781 C 7.548294 1.400384 0.324105 F 7.959610 2.304192 1.246793 F 8.446526 1.452568 0.688369 F 7.658679 0.180918 0.899677 C 3.375259 2.969527 3.251918 H 2.496129 3.340780 3.789517 H 3.112076 1.986994 2.846300 H 4.202014 2.854302 3.95356 8 TS12* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.07586838000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.19868154000 a.u Ru 0.930099 1.045510 0.665335 O 0.726480 0.468822 2.217268 O 1.056842 0.640298 1.666040 N 3.286150 2.565634 0.010859 N 3.908991 0.456851 0.045900 C 2.849133 1.292866 0.203624 C 4.668216 2.625188 0.474409 C 2.277642 3.618016 0.147668 C 1.949374 3.845492 1.645104 C 0.8016 27 4.864211 1.785291 C 1.224272 6.200807 1.143643 C 1.545472 5.973313 0.347965 C 2.712742 4.964274 0.474841 C 0.284892 5.429176 1.056312 C 0.134691 4.076452 0.419705 C 1.033988 3.096566 0.602295 C 0.446952 4.306483 1.072846 C 3.952308 0.942769 0.369167 C 4.069493 1.875380 0.681017 C 4.142143 3.234661 0.360777 C 4.145844 1.439815 2.126764 C 5.169072 1.206215 0.151469 C 3.9610 12 1.360764 1.713638 C 4.100896 3.688639 0.962777 C 4.024937 2.733574 1.979792 C 3.910132 0.385652 2.867352 C 4.124834 5.166146 1.278621 H 1.294663 3.094872 1.691497 H 5.244553 3.402398 0.03 5171 H 4.692548 2.830623 1.553446 H 1.663791 2.888513 2.095643 H 2.842698 4.209542 2.172073 H 0.584042 5.017534 2.850503 H 2.101404 6.610866 1.663961 H 0.418580 6.940207 1.244601 H 1.846185 6.922302 0.810321 H 2.979611 4.812667 1.529292 H 3.602612 5.363548 0.033989 H 0.478304 5.295305 2.129285 H 0.532413 6.158301 0.968338 H 1.023221 3.689061 0.933052 H 0.758478 3.367257 1.544377 H 1.283753 5.011077 1.172845 H 4.236153 3.958054 1.168311 H 5.161529 1.121168 2.399598 H 3.477835 0.598511 2.335086 H 3.877668 2.264110 2.794280 H 5.765451 0.767542 0.955341 H 5.764533 1.17 9689 0.770792 H 4.020754 3.062335 3.016799 H 4.398959 0.565104 2.633052 H 4.405626 0.811165 3.745937 H 2.874319 0.166136 3.147788 H 3.115139 5.597328 1.248922 H 4.527509 5.354322 2.279218 H 4.733701 5.720852 0.556438 N 0.546812 0.266685 2.419835 O 1.177091 0.885354 3.245334 C 0.681923 3.952722 1.546714 H 1.640673 4.249111 1.125006 C 0.221604 5.117162 1.858877

PAGE 185

178 H 1.284130 4.860206 1.792387 H 0.038668 5.502044 2.868505 O 0.094596 6.237382 1.011513 C 0.250631 6.259918 0.309575 O 0.257530 7.097058 1.016822 C 0.393929 1.066700 3.554675 C 0.761671 2.000714 2.347119 C 0.913072 0.354051 1.619710 C 0.862588 0.360471 3.169535 H 0.866095 1.410028 4.479922 H 1.866225 0.550217 3.561573 C 1.507266 1.061171 1.361043 H 1.443866 1.382572 0.317403 C 0.452999 2.648172 1.735636 C 0.485906 0.558811 1.042775 H 1.475647 2.765953 2.662042 H 1.598612 1.107193 1.216332 H 1.245692 1.967838 1.430104 H 1.275022 0.346952 1.778337 H 0.200312 1.139735 3.562414 H 0.687 740 1.089951 3.727965 O 2.872836 1.112878 1.816946 C 3.921939 0.647025 1.078913 C 3.835821 0.137119 0.221114 C 5.171133 0.726399 1.718220 C 4.999136 0.278264 0.871485 H 2.887326 0.045784 0.7 33759 C 6.319588 0.308902 1.061971 H 5.213375 1.120516 2.728641 C 6.241326 0.198360 0.241902 H 4.926708 0.675891 1.878601 H 7.280617 0.367515 1.562875 C 7.492486 0.594159 0.967812 F 8.074028 0.458646 1.594606 F 8.425579 1.099764 0.125564 F 7.257565 1.527649 1.918007 C 1.277986 5.258857 0.799588 H 2.219533 5.356236 0.246690 H 0.921941 4.230994 0.675033 H 1.461414 5.451539 1.856713 TS14* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0493751600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1924919800 a.u Ru 1.074950 0.577015 0.290312 O 1.864543 2.070257 0.050034 O 0.699068 0.870752 1.48437 7 N 3.580560 1.830607 0.470608 N 3.906407 0.264064 1.008442 C 2.994547 0.610087 0.474154 C 4.870313 1.872484 1.167936 C 2.807266 3.022852 0.122564 C 2.299369 3.732080 1.405599 C 1.437605 4. 950814 1.026329 C 2.283426 5.938354 0.197711 C 2.784756 5.236887 1.081581 C 3.661078 4.027339 0.691422 C 1.575924 4.754085 1.906057 C 0.730178 3.753174 1.074658 C 1.613292 2.539902 0.722890 C 0.231968 4.463433 0.202047 C 3.901222 1.699791 0.969875 C 3.642389 2.407661 2.161343 C 3.680738 3.805163 2.129316 C 3.337102 1.689784 3.455386 C 5.213279 0.384403 1.262310 C 4.265414 2.380199 0.209813 C 3.980422 4.511956 0.959265 C 4.279153 3.779556 0.192936 C 4.689282 1.655000 1.469151 C 3.971714 6.022254 0.935859 H 2.026508 2.133073 1.686225 H 5.613386 2.445914 0.608317 H 4.755572 2.332182 2.158491 H 1.712042 3.019845 1.998241 H 3.154152 4.051494 2.018586 H 1.088955 5.442349 1.944159 H 3.135322 6.302793 0.789948 H 1.681191 6.816950 0.068617 H 3.388297 5.93 5701 1.675550 H 4.055257 3.530029 1.588293 H 4.523061 4.373532 0.102618 H 1.915268 4.279806 2.837531 H 0.954382 5.612550 2.195583 H 0.120030 3.443428 1.684617 H 0.384466 3.776104 0.788066 H 0.404743 5.314546 0.074396 H 3.472797 4.355799 3.044111 H 4.189399 1.090003 3.798771 H 2.489480 1.005034 3.352697 H 3.099899 2.406406 4.247092 H 5.609438 0.091200 2.238109 H 5.935147 0.078229 0.494115 H 4.536283 4.309382 1.107712 H 5.779993 1.526185 1.494089 H 4.416833 2.230954 2.359296 H 4.241564 0.661873 1.556406 H 3.036149 6.402482 0.505808 H 4.790666 6.418103 0.325485 H 4.06 5113 6.439575 1.943488 N 1.666586 1.723728 1.229672 O 2.341458 2.113391 2.180713 C 1.010093 1.422213 1.245801 H 2.049892 1.577616 1.525824 C 0.078811 1.600571 2.425944 H 0.251522 0.830563 3. 182493 H 0.972330 1.562487 2.139151 O 0.405370 2.906172 2.960097

PAGE 186

179 C 0.190756 3.385680 4.089568 O 0.146088 4.470605 4.499394 C 0.576884 2.782905 2.036851 C 0.664129 2.339031 0.547997 C 1.053849 0.385142 1.772513 C 0.887943 1.491248 2.856993 H 1.322229 3.555045 2.239231 H 1.820090 1.604304 3.416520 C 1.696346 1.193472 0.624860 H 1.821409 0.631983 0.297868 C 0.684283 1.830629 0.06597 8 C 0.325050 0.107113 1.370053 H 1.010910 3.144061 0.109774 H 1.665187 0.463061 2.099729 H 1.522723 2.140448 0.676154 H 0.991760 0.140852 2.242988 H 0.102091 1.241912 3.577175 H 0.406070 3.205546 2.268645 O 2.923294 1.829163 1.002607 C 4.138448 1.214062 0.894990 C 4.336479 0.137275 0.594121 C 5.242623 2.051667 1.125858 C 5.638777 0.633430 0.511319 H 3.504784 0.812843 0.434382 C 6.531529 1.544775 1.046793 H 5.062883 3.095421 1.363360 C 6.738866 0.194404 0.735631 H 5.788499 1.682309 0.277610 H 7.380736 2.195164 1.230942 C 8.134618 0.334636 0.590639 F 8.632211 0.13 0731 0.654451 F 8.994307 0.268254 1.447505 F 8.202335 1.665440 0.821080 C 1.244772 2.524038 4.757220 H 2.074789 2.305573 4.076291 H 0.831474 1.562171 5.080357 H 1.622930 3.063075 5.626048 8* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0651361100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2048762600 a.u Ru 1.080524 0.549214 0.160313 O 0.046329 1.707721 1.662931 O 0.881610 1.537234 0.337986 N 3.901392 1.087991 0.113501 N 3.773842 1.070154 0.456279 C 3.027961 0.047360 0.204634 C 5.284688 0.737229 0.452026 C 3.408251 2.466183 0.132579 C 3.475148 3.054260 1.567509 C 2.904344 4.486222 1.580124 C 3.709717 5.375689 0.612598 C 3.615491 4.796063 0.813299 C 4.222586 3.376803 0.822373 C 2.136426 4.734865 1.249206 C 1.334133 3.824298 0.275794 C 1.955927 2.421960 0.351573 C 1.429 746 4.433595 1.141303 C 3.362159 2.382146 0.868485 C 3.021250 2.588165 2.223876 C 2.695866 3.881146 2.638556 C 3.034495 1.451139 3.220777 C 5.227917 0.794031 0.449528 C 3.444235 3.462221 0.0 28106 C 2.724070 4.972044 1.759381 C 3.110479 4.741543 0.437983 C 3.902139 3.292647 1.459018 C 2.341456 6.354807 2.232909 H 1.952667 2.098608 1.423529 H 5.987800 1.132858 0.285933 H 5.558905 1.139923 1.435715 H 2.902729 2.411638 2.247231 H 4.516552 3.066855 1.917060 H 2.974036 4.889017 2.598779 H 4.761188 5.432563 0.928411 H 3.315506 6.400263 0.628923 H 4.179844 5.429205 1.510203 H 4.203922 2.950581 1.834541 H 5.274782 3.422752 0.506479 H 2.058505 4.356306 2.277714 H 1.702927 5.744213 1.247025 H 0.290646 3.788535 0.603101 H 0.845344 3.844309 1.851886 H 1.004973 5.4 46351 1.126593 H 2.425824 4.044877 3.679686 H 2.335318 0.652716 2.949727 H 2.763723 1.811047 4.217583 H 4.029340 0.993114 3.293114 H 5.705784 1.244173 1.324173 H 5.686468 1.224258 0.449258 H 3.159734 5.578058 0.256075 H 4.957014 3.578124 1.569041 H 3.325139 3.933446 2.133649 H 3.800048 2.261423 1.804005 H 1.250582 6.471328 2.270853 H 2.730799 7.129524 1.564899 H 2.722244 6.551753 3.241214 C 1.010165 0.685454 1.748582 H 1.943024 1.095822 2.140338 N 0.999382 1.989552 0.874837 O 1.977160 2.643185 1.208189 C 1.397419 2.792543 1.436708 C 1.284865 1.277833 1.084200 C 1.0 05173 2.302588 0.929710 C 1.169525 3.491826 0.057596 H 2.391804 3.016879 1.833103 H 2.034955 4.096877 0.223723 C 1.959939 1.268015 0.311403

PAGE 187

180 H 1.949362 0.294371 0.797614 C 0.202726 1.050769 0 .767945 C 0.400632 1.695755 0.674365 H 1.704928 0.612967 1.842002 H 1.192097 2.556589 1.974020 H 0.842157 1.491934 1.528033 C 0.146855 0.242527 2.909855 H 0.632785 0.597976 3.422396 O 0.040749 1.352706 3.838360 C 0.691518 1.268192 4.984459 O 0.698371 2.213141 5.736702 C 1.466860 0.010560 5.239886 H 0.809869 0.887140 5.251791 H 2.220111 0.177889 4.461604 H 1.964486 0.081640 6.205473 H 1.150228 2.479080 0.575903 H 0.846683 0.081068 2.590638 O 3.282745 1.812634 0.341981 C 4.364247 1.054361 0.005519 C 5.596994 1.728020 0.040240 C 4.322501 0.301137 0.344356 C 6.76948 3 1.057614 0.276097 H 5.607415 2.775808 0.323253 C 5.508450 0.964753 0.660150 H 3.393661 0.855070 0.374724 C 6.733676 0.297707 0.629764 H 7.718755 1.582490 0.241363 H 5.467502 2.015567 0.927 787 C 7.994248 1.000735 1.034778 F 8.250737 0.867176 2.360642 F 7.941548 2.329328 0.785655 F 9.078018 0.510351 0.386086 H 0.661110 3.087688 2.190993 H 0.289152 4.143028 0.051884 9* B3LYP/SDD/6 31 G(d) SCF energy in gas p hase: 2563.0678407500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2090832000 a.u Ru 0.739353 0.658727 0.289866 O 0.569958 0.689849 2.848141 O 1.080970 0.339863 1.471165 N 2.456742 2.690218 0.795042 N 3.566556 0.847580 1.208655 C 2.437328 1.349015 0.620245 C 3.516641 3.156571 1.691629 C 1.303185 3.478274 0.351864 C 0.255096 3.634384 1.484041 C 0.990466 4.366106 0.944824 C 0.576303 5.765247 0.445451 C 0.473559 5.622293 0.675668 C 1.718973 4.890035 0.126159 C 0.137552 4.817079 1.840231 C 0.549336 3.404100 1.347503 C 0.724875 2.695469 0.851117 C 1.589863 3.548 400 0.217427 C 4.178613 0.426188 0.945871 C 4.253295 1.382701 1.974354 C 4.838197 2.623169 1.689771 C 3.729484 1.098216 3.363515 C 4.433571 1.925618 1.742567 C 4.761993 0.671941 0.316191 C 5.366851 2.923747 0.432058 C 5.343298 1.921450 0.546092 C 4.734798 0.360891 1.421022 C 5.912776 4.294284 0.113614 H 1.477475 2.706449 1.651027 H 4.018831 4.043434 1.296217 H 3.105969 3.406646 2.679402 H 0.018338 2.644029 1.865893 H 0.693673 4.199244 2.319336 H 1.728261 4.464794 1.751758 H 0.168434 6.358459 1.276239 H 1.453838 6.306518 0.067681 H 0.775203 6.616753 1.029237 H 2.489732 4.803792 0.903555 H 2.150511 5.468809 0.703872 H 0.581713 4.729896 2.665339 H 1.016304 5.344701 2.235963 H 0.993069 2.862699 2.186397 H 1.902118 2.556431 0.132471 H 2.488684 4.048993 0.602213 H 4.870489 3.377626 2.472624 H 4.441802 0.494504 3.942299 H 2.785073 0.546389 3.341212 H 3.572213 2.028397 3.917711 H 4.773507 1.684871 2.753218 H 5.318190 2.042068 1.103697 H 5.78 0444 2.123611 1.521736 H 5.102336 1.337498 1.085773 H 5.362879 0.041806 2.258107 H 3.719233 0.520104 1.803515 H 5.189539 4.854318 0.492927 H 6.845204 4.231855 0.459189 H 6.108718 4.870983 1. 022970 N 0.673019 0.497303 2.698943 O 1.468677 0.457391 3.623725 C 1.370428 1.266230 0.681467 H 2.455073 1.344152 0.702515 C 0.797953 2.108565 1.806806 H 1.074436 1.692254 2.774849 H 0.286645 2.203454 1.769996 O 1.300271 3.462482 1.658258 C 2.417854 3.903968 2.291726 O 2.925896 4.936608 1.916446 C 0.421405 2.750149 2.513076 C 0.327087 2.478798 0.987408 C 1.257718 0.570604 1.81498 5 C 1.104931 1.462898 3.078164

PAGE 188

181 H 1.037361 3.633932 2.696507 H 2.083073 1.693609 3.509613 C 1.588725 1.636248 0.743182 H 1.663033 1.242133 0.267742 C 0.831332 1.472112 0.752277 C 0.160631 0. 104243 1.438824 H 0.238400 3.383176 0.383309 H 1.982266 0.240941 1.924660 H 1.696191 1.696921 1.375415 H 0.732447 0.172339 2.329719 H 0.509228 0.966646 3.852137 H 0.564883 2.938450 2.950878 O 2.743235 2.422691 1.046952 C 3.986816 1.939098 0.766729 C 4.250075 0.759911 0.055672 C 5.053736 2.722489 1.237355 C 5.572904 0.381970 0.177667 H 3.447223 0.144330 0.332562 C 6.364271 2.334155 1.001190 H 4.826875 3.630375 1.787116 C 6.634207 1.155963 0.292503 H 5.773802 0.530791 0.728993 H 7.183168 2.940308 1.375482 C 8.052241 0.769610 0.004627 F 8.526839 1.378944 1.119024 F 8.889905 1.112849 1.003460 F 8.186644 0.561784 0.204924 C 2.945150 3.108820 3.473257 H 2.177253 2.985436 4.244873 H 3.279371 2.108968 3.177611 H 3.789349 3.658129 3.891067 10* B3LYP/SDD/6 31G( d) SCF energy in gas p hase: 2563.0709864700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2039785400 a.u Ru 0.662311 0.558466 0.185555 O 1.240328 0.145745 2.400741 O 0.755357 0.339542 1.695527 N 1.978912 3.02 2522 0.569573 N 3.383299 1.420675 1.097585 C 2.145881 1.678275 0.575164 C 3.051345 3.752593 1.248117 C 0.720525 3.587999 0.076695 C 0.218282 3.979680 1.245786 C 1.585345 4.430010 0.698009 C 1.386478 5.663720 0.204466 C 0.442000 5.296791 1.366069 C 0.929569 4.852011 0.795972 C 1.091131 4.159277 2.185875 C 1.273801 2.903410 1.290355 C 0.135843 2.483292 0.831041 C 2.197720 3.267278 0.111233 C 4.103820 0.184186 0.972007 C 4.282994 0.626233 2.106603 C 4.975890 1.835224 1.961903 C 3.746954 0.215191 3.459304 C 4.130787 2.663476 1.391550 C 4.672442 0.171200 0.271114 C 5.50 3465 2.244523 0.734360 C 5.358334 1.385564 0.362919 C 4.533184 0.708072 1.493951 C 6.193213 3.577702 0.570597 H 0.765170 2.473137 1.735605 H 3.391437 4.607873 0.657025 H 2.711608 4.125947 2. 223579 H 0.348584 3.133065 1.923381 H 0.243397 4.791061 1.827366 H 2.244448 4.687772 1.537601 H 0.969723 6.495754 0.380661 H 2.352256 6.004059 0.601489 H 0.287823 6.173497 2.008491 H 1.630311 4.627100 1.610593 H 1.361967 5.674358 0.206470 H 0.470737 3.910558 3.056950 H 2.062925 4.497254 2.572770 H 1.728021 2.100164 1.881064 H 2.346827 2.396615 0.540466 H 3.187671 3.555916 0.49038 3 H 5.094852 2.478050 2.831409 H 4.333317 0.606826 3.891340 H 2.710150 0.132463 3.401214 H 3.792036 1.050238 4.165064 H 4.566634 2.625347 2.393865 H 4.947987 2.793269 0.671034 H 5.776176 1. 681516 1.322728 H 4.823100 1.745369 1.291589 H 5.172073 0.339331 2.301944 H 3.503772 0.728652 1.867251 H 5.661827 4.195450 0.163712 H 7.220449 3.452370 0.206294 H 6.235781 4.126132 1.516751 N 0.071235 0.311000 2.683373 O 0.230111 0.704337 3.795673 C 1.620216 2.136350 0.190057 H 2.606607 1.723529 0.380698 C 1.129230 3.088958 1.249905 H 0.837789 2.595339 2.177849 H 0.278803 3.68217 9 0.907005 O 2.191688 4.037052 1.490583 C 3.133775 3.835876 2.456860 O 4.164840 4.465517 2.387878 C 0.303526 2.374459 3.115422 C 0.211363 2.523582 1.576100 C 1.277452 0.403229 1.940420 C 0.937868 0.972023 3.359600 H 0.947602 3.158077 3.521832 H 1.848394 1.061126 3.958634 C 1.408664 1.680988 1.087888

PAGE 189

182 H 1.394059 1.514770 0.011911 C 1.089900 1.958042 1.040979 C 0.208601 0.561317 1.457386 H 0.335957 3.564138 1.255830 H 2.227997 0.150894 1.964447 H 1.696418 1.410087 1.754350 H 0.032243 1.254780 2.279217 H 0.263879 0.299253 3.900927 H 0.677566 2.480275 3.590451 O 2.587 892 2.416366 1.456657 C 3.809026 2.020920 0.995189 C 4.018706 1.054732 0.000939 C 4.909972 2.669287 1.579436 C 5.321721 0.750492 0.396085 H 3.189419 0.547336 0.477291 C 6.200127 2.357245 1.1 76854 H 4.725152 3.411629 2.349267 C 6.415885 1.390157 0.185984 H 5.481158 0.001166 1.164421 H 7.046061 2.856035 1.639186 C 7.811804 1.093705 0.276325 F 8.241881 1.982206 1.205306 F 8.700729 1.148023 0.744255 F 7.913372 0.133348 0.836189 C 2.820090 2.875500 3.587262 H 1.884135 3.141560 4.090746 H 2.714679 1.842770 3.238277 H 3.640589 2.928701 4.303533 11* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.07628872000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.20068570000 a.u Ru 0.789243 0.965970 0.632058 O 0.836904 0.697701 2.049988 O 1.091814 0.208157 1.639321 N 2.875457 2.873031 0.09534 1 N 3.815748 0.890606 0.048779 C 2.641494 1.535829 0.178076 C 4.226611 3.187606 0.378020 C 1.717219 3.769297 0.032666 C 1.330614 4.065709 1.438802 C 0.038069 4.903515 1.486034 C 0.262231 6. 232270 0.737229 C 0.641992 5.936163 0.728433 C 1.952258 5.111749 0.763163 C 0.507943 5.148848 1.395875 C 0.726091 3.804313 0.651320 C 0.582436 3.005611 0.747009 C 1.097217 4.104215 0.815152 C 4.081452 0.506766 0.154906 C 4.329165 1.317443 0.969033 C 4.622261 2.670526 0.764993 C 4.316236 0.753829 2.371965 C 4.943028 1.839860 0.181775 C 4.180219 1.027719 1.460592 C 4.680850 3.23195 2 0.515190 C 4.469362 2.387823 1.610171 C 3.993778 0.169000 2.690635 C 4.956871 4.703982 0.715920 H 0.861549 2.957284 1.830202 H 4.681559 3.995672 0.201706 H 4.208262 3.491009 1.433755 H 1. 188828 3.117156 1.969589 H 2.147717 4.606914 1.936500 H 0.220583 5.108373 2.533264 H 1.056325 6.813851 1.226498 H 0.649135 6.843948 0.771715 H 0.803573 6.879118 1.266486 H 2.259180 4.917754 1.799641 H 2.760670 5.683894 0.284362 H 0.277092 4.959241 2.452914 H 1.428300 5.748572 1.373118 H 1.535804 3.243914 1.134617 H 1.271591 3.170669 1.361976 H 2.033252 4.678253 0.850487 H 4.814650 3.301089 1.630742 H 5.237775 0.197818 2.593237 H 3.481578 0.062786 2.527738 H 4.241816 1.556189 3.112209 H 5.587108 1.569340 1.022207 H 5.549935 1.824890 0.733172 H 4.538127 2.797841 2.615607 H 4.355003 0.853975 2.543974 H 4.536003 0.598415 3.539030 H 2.936758 0.110195 2.971598 H 4.037470 5.251559 0.960697 H 5.658096 4.867488 1.542216 H 5.382912 5.157694 0.184789 N 0.443 663 0.684782 2.294893 O 0.961454 1.455358 3.071845 C 1.030958 3.625414 1.610009 H 2.060621 3.840684 1.331493 C 0.066942 4.751069 1.326858 H 0.879487 4.395468 0.903608 H 0.175245 5.306679 2.2 40326 O 0.674249 5.735599 0.474873 C 0.857821 5.512481 0.859894 O 1.589719 6.261922 1.464283 C 0.472272 0.892833 3.797495 C 0.590442 1.957224 2.657653 C 1.005886 0.262652 1.680771 C 1.015217 0.445185 3.221807 H 1.038091 1.197262 4.682530 H 2.042021 0.615222 3.558686 C 1.415691 1.232091 1.562364 H 1.279397 1.649140 0.560717 C 0.754670 2.441258 2.166527 C 0.373822 0.576364 1.107328

PAGE 190

183 H 1.185747 2.813762 2.989745 H 1.762488 0.879880 1.184909 H 1.587785 1.754249 2.292633 H 1.167883 0.524522 1.865719 H 0.420015 1.308798 3.538054 H 0.572463 0.794095 4.112540 O 2.777845 1.4 10151 1.997766 C 3.853488 1.096864 1.219201 C 3.792639 0.686337 0.117327 C 5.100271 1.233648 1.852817 C 4.977106 0.420944 0.806235 H 2.847982 0.557468 0.629116 C 6.270762 0.967123 1.157145 H 5.123419 1.550549 2.890636 C 6.217075 0.555515 0.180828 H 4.924145 0.096744 1.840678 H 7.230266 1.068289 1.653840 C 7.483685 0.317959 0.948104 F 7.928180 1.442208 1.562463 F 8.489608 0.103554 0.144958 F 7.323623 0.612318 1.917456 C 0.117916 4.360677 1.507310 H 0.962217 4.428610 1.335549 H 0.462426 3.398081 1.114986 H 0.310432 4.389371 2.579442 12* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0764186000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1987602000 a.u Ru 1.513749 0.726033 0.694557 O 0.615008 0.132849 2.585603 O 0.295834 1.794256 1.525282 N 4.289174 0.458400 0.020196 N 3.598454 1.559828 0.513306 C 3.211718 0.264400 0.391793 C 5.439026 0.383348 0.366429 C 4.045845 1.813349 0.526687 C 3.854373 1.801000 2.064732 C 3.471571 3.209280 2.559506 C 4.594894 4.199486 2.192270 C 4.783189 4.215778 0.661198 C 5.183008 2.800652 0.176853 C 3.460063 4.657658 0.003146 C 2.330962 3.653950 0.354972 C 2.751358 2.275598 0.173721 C 2.150381 3.634057 1.886079 C 2.83 1356 2.634070 1.078391 C 2.346184 3.641390 0.220315 C 1.621627 4.699234 0.778124 C 2.619291 3.621291 1.266686 C 5.049750 1.723935 0.282229 C 2.641672 2.712596 2.471290 C 1.378936 4.786401 2.153178 C 1.908454 3.791075 2.978724 C 3.205020 1.683065 3.423318 C 0.559932 5.918349 2.727702 H 3.001125 2.397715 1.258638 H 6.372990 0.022354 0.032661 H 5.541647 0.472612 1.456474 H 3.07080 7 1.079783 2.322089 H 4.782463 1.472427 2.553312 H 3.341837 3.185148 3.649591 H 5.532294 3.909221 2.687517 H 4.343456 5.206884 2.549987 H 5.581912 4.919780 0.394409 H 5.352393 2.796819 0.908 047 H 6.126006 2.499328 0.656487 H 3.580924 4.714275 1.093573 H 3.192111 5.666361 0.340423 H 1.396380 3.964159 0.128044 H 1.347221 2.941322 2.162647 H 1.852781 4.631354 2.237684 H 1.245186 5.480650 0.120848 H 3.615747 4.023173 1.497768 H 2.577618 2.607599 1.676171 H 1.890986 4.235889 1.803784 H 5.249814 2.585918 0.359312 H 5.562434 1.883526 1.239949 H 1.754281 3.854844 4.053795 H 4.160723 1.275949 3.078191 H 3.364909 2.126348 4.411363 H 2.512570 0.843610 3.546336 H 0.504309 5.652075 2.769853 H 0.873538 6.161825 3.748270 H 0.643887 6.825099 2.119463 N 0.321785 1.043 962 2.565678 O 1.134648 1.154871 3.453966 C 1.586154 3.953375 1.697189 H 1.116693 4.755666 1.129070 C 2.717323 4.414000 2.575361 H 3.363582 3.591450 2.896976 H 2.328362 4.895714 3.479745 O 3.483086 5.457942 1.945591 C 4.440997 5.195175 1.008028 O 4.968396 6.129871 0.456238 C 0.583400 0.974113 3.397748 C 1.571631 1.468804 2.284956 C 0.474752 0.643517 1.565067 C 0.330606 0.521348 3.106571 H 0.995162 1.137337 4.398613 H 1.099011 1.138150 3.584301 C 1.726522 0.254511 1.323345 H 1.855165 0.551158 0.277676 C 1.098673 2.711260 1.577868 C 0.790304 0.140331 0.883647 H 2.557794 1.642209 2.722753 H 0.699794 1.665119 1.242870 H 0.248994 2.575463 0.908925

PAGE 191

184 H 1.266748 0.684730 1.430430 H 0.644735 0.862459 3.469372 H 0.352153 1.542354 3.347891 O 2.914042 0.415259 1.787812 C 3.662329 1.215368 0.972408 C 3.286787 1.632370 0.308126 C 4.894823 1.625650 1.507365 C 4.148561 2.441094 1.049777 H 2.323850 1.373709 0.725200 C 5.743366 2.432742 0.762894 H 5.16 4393 1.297697 2.506291 C 5.376608 2.844627 0.525334 H 3.843388 2.764565 2.039458 H 6.692861 2.749954 1.182121 C 6.322850 3.667198 1.348626 F 7.193750 2.896798 2.046936 F 7.074041 4.492266 0. 580154 F 5.675150 4.435542 2.253205 C 4.805970 3.748422 0.736407 H 5.230579 3.274154 1.629026 H 3.932689 3.163034 0.432004 H 5.551846 3.733648 0.058486 13* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0775645900 0 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2019279100 a.u Ru 2.183462 0.585792 0.703871 O 1.203015 0.359771 2.617422 O 0.843024 2.214376 1.542933 N 4.669474 0.632558 0.084611 N 3.33 7664 2.274408 0.526499 C 3.424144 0.927477 0.381912 C 5.434641 1.830494 0.446511 C 4.874761 0.707687 0.646943 C 4.606813 0.708388 2.173618 C 4.695802 2.144862 2.724759 C 6.105438 2.707298 2. 452357 C 6.370599 2.711154 0.932599 C 6.295666 1.261703 0.392737 C 5.311647 3.597983 0.240530 C 3.892670 3.026278 0.504250 C 3.849656 1.605690 0.076977 C 3.635287 3.017935 2.024249 C 2.255057 2.997363 1.132583 C 1.403958 3.757638 0.306819 C 0.361714 4.474130 0.904169 C 1.610154 3.840532 1.188381 C 4.629656 2.939765 0.255422 C 2.098379 2.994638 2.531912 C 0.155507 4.463928 2.28731 3 C 1.041591 3.729261 3.080189 C 3.028236 2.229326 3.444432 C 0.996837 5.217858 2.909069 H 4.181457 1.675209 1.143789 H 6.468322 1.773004 0.093738 H 5.451175 1.968130 1.536256 H 3.612135 0.289212 2.363067 H 5.341319 0.068067 2.682054 H 4.507689 2.127465 3.806457 H 6.862262 2.100572 2.969420 H 6.188647 3.727965 2.849157 H 7.373088 3.111328 0.733244 H 6.511687 1.238114 0.683686 H 7.054646 0.641316 0.892260 H 5.502147 3.646590 0.840171 H 5.383103 4.625562 0.623478 H 3.144775 3.651351 0.001305 H 2.631135 2.633368 2.235476 H 3.676355 4.044338 2.413846 H 0.299799 5.06 1988 0.270937 H 2.434985 4.519510 1.444970 H 1.851408 2.865686 1.622790 H 0.713238 4.224384 1.683627 H 4.491679 3.828588 0.365694 H 5.094421 3.250630 1.200419 H 0.912740 3.727888 4.160531 H 4.061197 2.231188 3.081619 H 3.022626 2.666043 4.448098 H 2.711218 1.185054 3.536013 H 1.849775 4.551642 3.093960 H 0.715517 5.655540 3.873109 H 1.347074 6.025672 2.258196 N 0.615151 1.534532 2.602103 O 0.070389 1.915552 3.521027 C 3.045197 2.422324 1.116853 H 2.949788 3.397873 0.642784 C 4.430155 2.113448 1.603447 H 5.115398 1.999864 0.752109 H 4.465524 1.189492 2.188464 O 4.84 9267 3.232072 2.411719 C 6.102149 3.297287 2.944237 O 6.396928 4.263000 3.605823 C 0.877780 0.250429 3.049145 C 1.844879 0.273007 1.822741 C 0.143362 1.169401 1.356847 C 0.030173 1.024474 2. 889061 H 1.427383 0.281782 3.995231 H 0.574637 1.896201 3.270253 C 1.266141 0.793408 0.828803 H 1.232837 0.443286 0.207391 C 1.960620 1.642146 1.208080 C 1.231484 0.253481 0.820546 H 2.829333 0.086330 2.133554 H 0.343874 2.200857 1.053149 H 1.032864 2.034016 0.788400 H 1.364239 0.671592 1.398167 H 0.924720 0.969370 3.423537 H 0.237323 1.140425 3.031349

PAGE 192

185 O 2.033935 2.008510 0.892210 C 3.232777 2.097142 0.256916 C 3.829147 1.067109 0.485596 C 3.888020 3.334789 0.376314 C 5.063841 1.285360 1.098321 H 3.346795 0.102812 0.591892 C 5.117482 3.537674 0.232529 H 3.4054 02 4.122658 0.945394 C 5.716416 2.512026 0.976266 H 5.515389 0.491300 1.684654 H 5.612738 4.499004 0.142262 C 7.074464 2.709828 1.580720 F 8.068024 2.356973 0.724789 F 7.297587 4.000882 1.91 5629 F 7.247510 1.963665 2.695930 C 7.053903 2.146794 2.673370 H 6.644455 1.193168 3.024564 H 7.257142 2.039419 1.601839 H 7.988968 2.351235 3.195114 TS9E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0453651400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1818100900 a.u Ru 0.799462 0.599161 0.107810 O 0.091661 1.553108 1.784278 O 1.268202 1.424170 0.032697 N 3.560227 1.450733 0.125047 N 3.612510 0.693418 0.607459 C 2.779682 0.342886 0.243367 C 4.946375 1.258534 0.558886 C 2.931771 2.777346 0.044768 C 2.783004 3.395018 1.460822 C 2.057648 4.753665 1.369783 C 2.858461 5.709371 0.464134 C 2.981221 5.091606 0.943368 C 3.747967 3.752433 0.836359 C 1.566588 4.861025 1.522490 C 0.773586 3.879472 0.614362 C 1.558696 2.547595 0.608611 C 0.651510 4.530228 0.780955 C 3.26 4590 1.941454 1.231077 C 2.870871 1.935777 2.588861 C 2.594348 3.156174 3.210053 C 2.771737 0.650658 3.380643 C 5.026879 0.265553 0.717867 C 3.450578 3.156172 0.545284 C 2.726108 4.378371 2. 539512 C 3.170199 4.354166 1.216532 C 3.919805 3.220282 0.891623 C 2.400733 5.680732 3.232682 H 1.767151 2.334784 1.665954 H 5.650231 1.639621 0.186849 H 5.136741 1.785151 1.502915 H 2.215796 2.708761 2.098759 H 3.773650 3.536314 1.916721 H 1.974208 5.181781 2.377319 H 3.857017 5.892602 0.886610 H 2.353117 6.682690 0.405468 H 3.542502 5.770637 1.598911 H 3.895580 3.309583 1.831046 H 4.745183 3.937086 0.408952 H 1.635640 4.460375 2.543470 H 1.038717 5.822554 1.593403 H 0.223918 3.718960 1.038640 H 0.062654 3.915443 1.464023 H 0.130422 5.493316 0.688157 H 2.28436 8 3.153162 4.252998 H 3.718191 0.096164 3.368814 H 2.003452 0.025165 2.989615 H 2.527646 0.863345 4.425480 H 5.442951 0.574343 1.681355 H 5.628497 0.733475 0.071100 H 3.309917 5.293322 0.685 240 H 4.471539 4.148179 1.072453 H 3.074180 3.211079 1.591501 H 4.571892 2.383291 1.155206 H 1.317314 5.856457 3.254949 H 2.860282 6.532664 2.721690 H 2.748103 5.679134 4.271800 N 1.214885 1.776782 1.205697 O 2.164797 2.282956 1.778090 C 0.801609 0.208980 1.803196 C 1.274829 3.680490 0.090567 C 0.986655 2.465218 0.856133 C 1.605279 1.471140 1.091231 C 1.721471 2.997086 1.421118 H 2.078082 4.289271 0.332244 H 2.756219 3.252352 1.666475 C 2.066724 1.472299 0.391015 H 2.003352 0.496617 0.871160 C 0.271662 1.844534 0.265782 C 0.103758 1.234094 0.946990 H 0.958932 2.706 770 1.918996 H 2.139624 0.817201 1.781816 H 1.233378 2.312926 0.417189 H 0.528743 1.257869 1.825527 H 1.093589 3.270889 2.274478 H 0.392088 4.316559 0.208467 O 3.353376 2.042216 0.617898 C 4.478484 1.295571 0.410482 C 4.490322 0.032880 0.034206 C 5.689246 1.956109 0.674611 C 5.711896 0.684214 0.208551 H 3.575258 0.570348 0.247433 C 6.897313 1.296862 0.497496 H 5.655741 2.985887 1.015830 C 6.917162 0.030988 0.051433 H 5.715381 1.709915 0.562644

PAGE 193

186 H 7.830056 1.814771 0.696416 C 8.221337 0.757995 0.087310 F 8.601875 1.352225 1.071555 F 9.230056 0.075751 0.437876 F 8.163266 1.735782 1.019895 C 1.890941 0.717917 2.691069 H 2.799482 0.963907 2.137057 H 2.123321 0.104690 3.386184 O 1.435451 1.880668 3.416745 C 2.048159 2.321411 4.555292 O 1.655129 3.343744 5.060110 C 3.179793 1.486418 5.125521 H 3.967138 1.304360 4.386187 H 2.814659 0.510823 5.467209 H 3.597634 2.024062 5.976902 H 0.164200 0.218514 2.333110 TS10E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase : 2563.0476017000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution : 2562.1955956500 a.u Ru 0.925920 0.677553 0.315195 O 1.084809 1.139614 1.005312 O 2.380057 2.740059 0.270437 N 3.602159 1.566123 0.262731 N 3. 751249 0.600268 0.593140 C 2.883646 0.412926 0.260656 C 4.988139 1.415054 0.715625 C 2.890256 2.846409 0.310935 C 2.592304 3.233924 1.787408 C 1.783400 4.543226 1.841047 C 2.599944 5.667787 1.171097 C 2.893040 5.290121 0.295924 C 3.710630 3.982593 0.343841 C 1.564199 5.081649 1.042986 C 0.742861 3.947715 0.370821 C 1.562193 2.648103 0.439323 C 0.453602 4.336095 1.092931 C 3.4631 10 1.904198 1.136061 C 3.042183 1.991167 2.485079 C 2.810010 3.252820 3.034613 C 2.894811 0.760933 3.353939 C 5.140031 0.110322 0.769836 C 3.751727 3.068908 0.401927 C 3.017823 4.430411 2.30 3703 C 3.507396 4.312871 1.003372 C 4.326577 3.052006 0.996822 C 2.731041 5.781388 2.915262 H 1.783562 2.408522 1.508548 H 5.685231 1.879541 0.012767 H 5.132504 1.885309 1.696865 H 2.029065 2.419415 2.261452 H 3.533505 3.350171 2.342760 H 1.589142 4.801718 2.890171 H 3.539682 5.832415 1.717381 H 2.040032 6.611385 1.208242 H 3.472329 6.089575 0.775667 H 3.948010 3.713994 1.382128 H 4.664778 4.119233 0.185372 H 1.750567 4.835487 2.097051 H 0.974518 6.007988 1.033286 H 0.187403 3.854240 0.922659 H 0.147292 3.556135 1.576405 H 0.143601 5.256601 1.117550 H 2.475855 3.319971 4.067773 H 3.858692 0.255403 3.498805 H 2.208830 0.021951 2.928835 H 2.519803 1.034945 4.344213 H 5.547987 0.467758 1.719311 H 5.778411 0.491980 0.035437 H 3.717762 5.213687 0.430678 H 5.130673 3.791411 1.081607 H 3.569812 3.311387 1.746395 H 4.739141 2.077063 1.265899 H 1.655469 5.999901 2.899776 H 3.236741 6.583760 2.369196 H 3.053925 5.824391 3.961458 N 1.718187 2.27 3649 1.205008 O 1.643482 2.790028 2.324372 C 0.779316 0.716647 1.765540 H 0.119611 0.499803 2.348166 C 1.956294 1.062580 2.646581 H 2.881596 1.104868 2.075321 H 2.073309 0.312449 3.434606 O 1.824948 2.385326 3.221430 C 1.200910 2.626739 4.413172 O 1.069518 3.774401 4.761870 C 0.739466 1.443181 5.243151 H 1.591698 0.838031 5.573859 H 0.059960 0.786747 4.690351 H 0.225280 1.835050 6.120924 C 0.813782 3.480072 0.560932 C 0.818514 2.477675 0.624557 C 1.261270 1.161049 1.175853 C 1.178112 2.589400 1.793497 H 1.569214 4.252697 0.397220 H 2.145245 2.877342 2.214602 C 1.90 7334 1.485641 0.192785 H 2.005533 0.625844 0.848239 C 0.489910 1.633886 0.544912 C 0.189482 0.793477 0.829882 H 0.959768 2.940171 1.604359 H 1.780181 0.427327 1.796196 H 1.363028 2.260861 0. 371322 H 0.868890 1.097532 1.622025 H 0.432856 2.646670 2.593569 H 0.156090 3.977169 0.665766 O 3.155681 2.176065 0.097283 C 4.299400 1.462312 0.116011

PAGE 194

187 C 4.361682 0.068628 0.251973 C 5.475120 2.226692 0.198577 C 5.598947 0.542932 0.457862 H 3.476164 0.553670 0.198685 C 6.698026 1.606408 0.408546 H 5.401752 3.304660 0.094789 C 6.768741 0.213095 0.540738 H 5.640161 1.622319 0.560169 H 7.602191 2.202865 0.478576 C 8.100519 0.454167 0.709400 F 8.717441 0.675313 0.478441 F 8.953725 0.299986 1.445387 F 7.996895 1.656302 1.320311 TS11E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0589903000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1984014700 a.u Ru 0.728013 0.510608 0.374859 O 1.037257 0.059436 1.636888 O 0.778997 0.395783 2.781446 N 2.210268 2.758103 0.665544 N 3.48 0445 1.058029 1.203029 C 2.340438 1.415435 0.530334 C 3.169368 3.361918 1.593790 C 1.000095 3.430882 0.183867 C 0.042850 3.594222 1.318363 C 1.342582 4.195710 0.748811 C 1.038093 5.585096 0. 153258 C 0.010419 5.442599 0.968922 C 1.309804 4.837714 0.386929 C 0.554680 4.521854 2.069693 C 0.851345 3.118074 1.480250 C 0.477790 2.536533 0.959532 C 1.889001 3.259146 0.348623 C 4.272965 0.130151 1.047180 C 4.370584 1.037976 2.118175 C 5.213148 2.146910 1.977742 C 3.621342 0.823693 3.413258 C 4.194789 2.235305 1.753483 C 5.056700 0.292943 0.114470 C 5.978240 2.356092 0.82697 0 C 5.895755 1.408353 0.199119 C 4.979074 0.682850 1.266882 C 6.851200 3.579914 0.683889 H 1.216660 2.598678 1.772033 H 3.605015 4.277345 1.184252 H 2.679076 3.612634 2.543961 H 0.243508 2. 618201 1.772357 H 0.360662 4.248216 2.104822 H 2.079036 4.293906 1.557424 H 0.668098 6.260359 0.937905 H 1.956204 6.034876 0.247645 H 0.238314 6.430454 1.390192 H 2.079166 4.756765 1.166094 H 1.702885 5.502017 0.397001 H 0.158369 4.435195 2.900389 H 1.474132 4.959989 2.482832 H 1.264135 2.486274 2.271629 H 2.118071 2.272596 0.072714 H 2.828062 3.663572 0.750815 H 5.278529 2.86079 6 2.795880 H 3.654849 1.724761 4.032903 H 4.062853 0.008414 4.002005 H 2.572730 0.561847 3.245235 H 4.483465 2.058444 2.793087 H 5.108557 2.421211 1.175679 H 6.495301 1.544631 1.096620 H 5.184616 1.713373 0.954443 H 5.706620 0.421199 2.040668 H 3.983659 0.684557 1.726196 H 6.304524 4.391898 0.187116 H 7.740915 3.369608 0.080858 H 7.179931 3.955167 1.658532 N 0.467679 0.121949 2.800547 O 1.093929 0.074702 3.827092 C 1.100292 1.589901 0.785243 H 0.250936 1.921065 1.386008 C 2.413368 1.976446 1.416265 H 3.253859 1.715241 0.781307 H 2.534110 1.499279 2.390001 O 2.48 2913 3.419352 1.541461 C 2.113195 4.082885 2.673867 O 2.122382 5.290849 2.654034 C 1.746313 3.277902 3.908648 H 2.610272 2.715309 4.281319 H 0.943737 2.556561 3.725955 H 1.427774 3.982482 4. 677187 C 0.308492 2.558189 2.724140 C 0.309719 2.489881 1.173962 C 1.227586 0.486512 1.835836 C 1.023090 1.245069 3.171804 H 0.862782 3.438535 3.058873 H 1.985501 1.465364 3.641692 C 1.557843 1.649521 0.871494 H 1.638853 1.357425 0.173684 C 0.894170 1.696476 0.636795 C 0.117534 0.079190 1.386058 H 0.331914 3.478068 0.703384 H 1.996813 0.292607 1.879276 H 1.802586 1.782628 1.22877 4 H 0.759271 0.280595 2.253958 H 0.434705 0.656538 3.883923 H 0.709472 2.644976 3.118917 O 2.711694 2.393755 1.264174 C 3.956998 1.930421 0.951655 C 4.220924 0.824563 0.131996 C 5.022111 2. 655522 1.510523 C 5.544292 0.460253 0.120942

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188 H 3.419922 0.254710 0.323941 C 6.332863 2.281679 1.253398 H 4.793894 3.506865 2.143757 C 6.603742 1.176306 0.435997 H 5.746667 0.395951 0.755913 H 7.151212 2.841612 1.694827 C 8.024350 0.810766 0.122627 F 8.528186 1.547427 0.897502 F 8.841852 1.017774 1.182960 F 8.149565 0.487395 0.236434 TS12E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0797567100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2003542900 a.u Ru 0.095817 1.221240 0.639958 O 1.109444 0.271413 1.856555 O 0.991031 0.092888 2.268157 N 0.872424 3.830548 0.294643 N 2.709 903 2.622419 0.246914 C 1.373743 2.600575 0.007696 C 1.858878 4.715020 0.922802 C 0.583743 3.980011 0.374824 C 1.076551 3.835128 1.837590 C 2.616679 3.873360 1.880899 C 3.111871 5.214295 1.3 03051 C 2.625183 5.354196 0.154022 C 1.077279 5.335713 0.181650 C 3.194183 4.185009 0.988791 C 2.685494 2.834387 0.416293 C 1.152689 2.844697 0.501894 C 3.166683 2.702228 1.042598 C 3.673648 1.633324 0.154118 C 4.293593 0.849564 0.839808 C 5.277453 0.063810 0.452045 C 3.930147 0.989486 2.299926 C 3.175148 3.978540 0.615231 C 4.050879 1.525318 1.505562 C 5.675077 0.199361 0.883968 C 5.047002 0.600695 1.842070 C 3.414978 2.364797 2.589753 C 6.777151 1.161069 1.262636 H 0.884910 3.096025 1.560844 H 1.829543 5.722277 0.497420 H 1.677493 4.793473 2.003340 H 0.708225 2.888555 2.249434 H 0.662893 4.647896 2.451086 H 2.949954 3.773137 2.922186 H 2.738664 6.050366 1.911297 H 4.208580 5.258659 1.338015 H 2.974902 6.307621 0.570622 H 0.706887 5.468549 1.206894 H 0.687695 6.172219 0.417316 H 2.892904 4.285267 2.040481 H 4.292326 4.215560 0.967044 H 3.081427 2.006336 1.016643 H 2.830969 1.749326 1.466232 H 4.264687 2.699852 1.072648 H 5.745116 0.688 458 1.209266 H 4.399603 0.197448 2.890563 H 4.267775 1.949012 2.714234 H 2.848078 0.938466 2.457685 H 3.856632 3.939838 1.468958 H 3.712108 4.429131 0.229711 H 5.343071 0.511986 2.885177 H 3.237065 3.396946 2.269417 H 4.057071 2.395168 3.475459 H 2.450694 1.943467 2.895035 H 6.695902 2.095413 0.698599 H 6.752846 1.396098 2.331883 H 7.764054 0.731660 1.044240 N 0.096479 0.554094 2.593026 O 0.128768 1.341677 3.509250 C 2.450731 3.634428 0.444137 H 2.180152 4.630949 0.795454 C 3.647585 3.523682 0.452825 H 3.728825 2.512838 0.857357 H 3.584492 4.222819 1.293422 O 4.895 991 3.723781 0.260951 C 5.480335 4.942126 0.409906 O 6.517888 5.008890 1.025988 C 4.819011 6.152682 0.226572 H 4.842084 6.082114 1.320306 H 3.773221 6.263766 0.076359 H 5.380012 7.036204 0.0 78947 C 0.601409 1.834605 3.000084 C 0.480286 2.649708 1.668252 C 0.934581 0.624411 1.552446 C 0.633647 0.907391 3.045341 H 0.662241 2.493992 3.871127 H 1.485076 1.426051 3.497070 C 0.762041 2.048721 0.952416 H 0.679366 2.061303 0.136093 C 1.713669 2.581032 0.810716 C 0.027017 0.437190 1.014630 H 0.253434 3.699062 1.879348 H 1.967565 0.297463 1.385234 H 2.006847 1.589189 0.461471 H 0.772962 0.725144 1.768638 H 0.456540 0.008095 3.620967 H 1.524159 1.242832 2.989184 O 1.856409 2.886869 1.374170 C 3.093472 2.801965 0.806117 C 3.395899 2.105175 0.371204 C 4.105002 3.5 08009 1.478833 C 4.702130 2.126011 0.861399 H 2.636534 1.558325 0.915567 C 5.400034 3.521442 0.980422 H 3.848750 4.038316 2.390496

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189 C 5.709566 2.825032 0.194822 H 4.933294 1.583507 1.772708 H 6.177410 4.063662 1.508938 C 7.095479 2.879648 0.764731 F 7.249367 3.903842 1.640314 F 8.032951 3.052535 0.197089 F 7.411935 1.748500 1.437770 TS13E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0831055 1000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.19978962000 a.u Ru 1.655667 0.942955 0.452534 O 0.361844 2.790920 0.199237 O 0.139895 1.464257 1.907288 N 4.094652 0.489338 0.992870 N 2.449908 1.754824 1.726872 C 2.739642 0.578068 1.118883 C 4.775887 1.732942 1.367147 C 4.613187 0.513559 0.056035 C 4.784820 0.094079 1.360196 C 5.199116 1.003461 2.359330 C 6.535829 1.623737 1.905485 C 6.366673 2.231833 0.497812 C 5.964509 1.118254 0.500646 C 5.277032 3.325599 0.551394 C 3.927224 2.700646 0.995744 C 3.547528 1.629574 0.036839 C 4.100651 2.085626 2.398489 C 1.155585 2.185 096 2.181914 C 0.490189 3.200029 1.464864 C 0.768741 3.616882 1.906900 C 1.105935 3.851304 0.247044 C 3.673305 2.467052 2.151784 C 0.600008 1.635578 3.351365 C 1.364236 3.064412 3.047376 C 0.662053 2.087078 3.756612 C 1.312989 0.579583 4.164184 C 2.718798 3.546781 3.513063 H 3.574776 2.116742 1.043781 H 5.666858 1.540999 1.971937 H 5.081857 2.294883 0.473927 H 3.839764 0.554036 1.669874 H 5.547844 0.884958 1.336293 H 5.317935 0.557713 3.356001 H 7.324835 0.858248 1.896898 H 6.853055 2.400871 2.613920 H 7.316503 2.674117 0.170176 H 5.868241 1.526196 1.515619 H 6.749193 0.347645 0.530305 H 5.164675 3.800848 0.432585 H 5.579534 4.114669 1.254012 H 3.153187 3.477363 1.021444 H 3.153309 1.648743 2.735860 H 4.371643 2.870172 3.118508 H 1.292861 4.385622 1.343717 H 0.390520 4.530084 0.225115 H 1.992467 4.444913 0.508133 H 1.429256 3.111219 0.493548 H 3.611370 3.531777 1.913496 H 3.804899 2.366320 3.237381 H 1.103733 1.658307 4.654015 H 2.396 268 0.737363 4.192019 H 0.946887 0.580956 5.195888 H 1.133906 0.418908 3.751271 H 3.356609 3.812571 2.663464 H 3.235046 2.784479 4.106032 H 2.626107 4.443338 4.140833 N 0.230448 2.576203 1.3 12678 O 1.052260 3.315171 1.799973 C 3.550551 2.468439 2.551704 H 4.130456 1.939683 3.309249 C 4.286341 3.596186 1.877244 H 5.094177 3.203428 1.248841 H 4.755454 4.255477 2.617975 O 3.463833 4.349545 0.973708 C 2.655818 5.352805 1.406993 O 1.873851 5.839315 0.620366 C 2.791336 5.830234 2.839483 H 3.784501 6.257232 3.020000 H 2.642804 5.008204 3.546817 H 2.038915 6.600579 3.008859 C 0.229748 1.313833 3.554820 C 1.584071 0.930046 2.909789 C 0.259005 0.606785 2.139852 C 0.586329 0.012348 3.523514 H 0.358481 1.722427 4.562904 H 0.245275 0.664848 4.316933 C 1.241703 0.2 21453 1.903781 H 1.391342 0.096373 0.872389 C 2.305935 2.077898 2.264455 C 1.138474 0.031721 1.044600 H 2.224664 0.477615 3.675805 H 0.327229 1.697700 2.145663 H 1.754903 2.606985 1.486087 H 1.362863 1.036288 1.178944 H 1.659340 0.176809 3.671116 H 0.265518 2.089575 2.955827 O 2.071264 1.351693 2.201094 C 3.050250 1.794359 1.360758 C 3.274027 1.354232 0.049317 C 3.874278 2.796052 1.902807 C 4.311691 1.912773 0.697550 H 2.650892 0.598731 0.413902 C 4.903698 3.342802 1.152061 H 3.678618 3.131503 2.916185 C 5.132798 2.902031 0.157901 H 4.467820 1.579688 1.718047 H 5.5 28367 4.121505 1.578198

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190 C 6.283616 3.454959 0.942973 F 7.449973 2.820937 0.652965 F 6.491041 4.766845 0.680339 F 6.100205 3.331531 2.276394 TS14E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0445482300 a .u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1897178600 a.u Ru 0.927598 0.625909 0.299242 O 0.868297 1.309780 1.290049 O 1.863728 2.089380 0.519037 N 3.561487 1.547669 0.478642 N 3.727190 0.610321 0.801913 C 2.866771 0.387624 0.419526 C 4.961681 1.406152 0.891611 C 2.877577 2.838832 0.385312 C 2.577143 3.376453 1.811471 C 1.801499 4.703872 1.720150 C 2.649669 5.736766 0.950584 C 2.943265 5.207802 0.468797 C 3.732827 3.884511 0.371291 C 1.612912 4.961412 1.205686 C 0.765334 3.914499 0.435418 C 1.556155 2.597706 0.357233 C 0.473139 4.451871 0.981647 C 3.446979 1.974126 1.162615 C 2.976602 2.259826 2.464307 C 2.758288 3.593864 2.819368 C 2.782921 1.188492 3.516641 C 5.053103 0.092585 1.212837 C 3.796151 3.020139 0.283999 C 3.030075 4.650516 1.943284 C 3.56 4836 4.340329 0.691262 C 4.436970 2.785064 1.065895 C 2.756327 6.081115 2.343844 H 1.816662 2.291748 1.414682 H 5.636368 1.701998 0.080422 H 5.181465 2.037161 1.758949 H 1.986630 2.627172 2. 353083 H 3.517338 3.524994 2.361917 H 1.601346 5.072051 2.734936 H 3.590327 5.932359 1.485476 H 2.113428 6.692860 0.889271 H 3.546631 5.940975 1.019840 H 3.973849 3.505163 1.373998 H 4.685230 4.058956 0.150104 H 1.803641 4.612791 2.230303 H 1.051400 5.901810 1.290053 H 0.168567 3.767677 0.979141 H 0.145211 3.731980 1.527425 H 0.101605 5.384945 0.910258 H 2.383034 3.814219 3.816906 H 3.663380 1.131511 4.171377 H 2.627447 0.194584 3.091930 H 1.927250 1.419590 4.159452 H 5.216701 0.287055 2.279086 H 5.846713 0.599684 0.654938 H 3.823264 5.147091 0.008428 H 5.3133 77 3.432580 1.183624 H 3.751203 3.024390 1.887115 H 4.763532 1.750192 1.192744 H 1.716814 6.359161 2.125898 H 3.400863 6.779648 1.800729 H 2.914511 6.234182 3.416746 N 1.777392 2.075302 0.72 3148 O 2.510712 2.722267 1.468089 C 0.668853 0.879648 1.858760 H 0.239904 0.586789 2.385114 C 1.907412 0.924415 2.729786 H 2.813826 0.927432 2.126855 H 1.944208 0.061893 3.401440 O 1.982414 2.156575 3.486013 C 1.415462 2.314955 4.718784 O 1.470004 3.405320 5.232581 C 0.779972 1.108391 5.384412 H 1.530374 0.340013 5.604544 H 0.006465 0.648286 4.761493 H 0.335234 1.442942 6.321807 C 0.702174 3.234077 0.922033 C 0.811016 2.394391 0.382165 C 1.238642 0.878160 1.347154 C 1.081418 2.248999 2.068423 H 1.404120 4.070609 0.884215 H 2.031543 2.534513 2.527321 C 1.848637 1.32 0536 0.001243 H 1.954710 0.520649 0.732360 C 0.512823 1.754590 0.764347 C 0.136958 0.282639 1.147010 H 1.164880 2.995334 1.228525 H 1.863023 0.164150 1.896024 H 1.394631 2.282027 0.415366 H 0.767506 0.460890 2.023892 H 0.328896 2.211101 2.862012 H 0.302003 3.650809 1.044984 O 3.086331 2.026199 0.148872 C 4.282078 1.373084 0.241337 C 4.437728 0.008139 0.400988 C 5.413831 2.203554 0.177907 C 5.723698 0.546068 0.479575 H 3.586544 0.672392 0.483558 C 6.685873 1.657710 0.264495 H 5.267331 3.272421 0.058958 C 6.849846 0.273877 0.414019 H 5.839408 1.617679 0.601847 H 7.556319 2.304843 0.220605 C 8.229442 0.312791 0.448439 F 8.747134 0.476544 0.794425 F 9.098235 0.483155 1.119233

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191 F 8.254479 1.526852 1.042694 5E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0775645900 0 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2019279100 a.u Ru 0.905724 0.619387 0.206429 O 1.103983 1.512519 0.354309 O 0.198599 1.759242 1.608736 N 3.662064 1.344323 0.202925 N 3.649968 0.803685 0.651547 C 2.858431 0.250424 0.270057 C 5.067418 1.093491 0.530603 C 3.097276 2.688854 0.072710 C 3.036849 3.397974 1.453698 C 2.384270 4.788432 1.305417 C 3.199222 5.643260 0.315241 C 3.234 726 4.940649 1.057421 C 3.922059 3.566680 0.904642 C 1.794050 4.751009 1.577110 C 0.979655 3.879590 0.577870 C 1.684867 2.520880 0.491311 C 0.946597 4.610700 0.783438 C 3.246056 2.054989 1.239224 C 2.768034 2.055121 2.570840 C 2.437974 3.276734 3.160528 C 2.622530 0.775439 3.364916 C 5.053100 0.396839 0.904553 C 3.465619 3.263461 0.553983 C 2.593329 4.494112 2.484401 C 3.1220 40 4.463362 1.194124 C 4.056715 3.330746 0.836720 C 2.202427 5.797712 3.140237 H 1.766276 2.108029 1.527933 H 5.709640 1.299047 0.333169 H 5.400782 1.730587 1.356989 H 2.458353 2.780139 2.14 9903 H 4.051733 3.502092 1.862540 H 2.363919 5.277597 2.287659 H 4.221679 5.795218 0.689216 H 2.744654 6.637852 0.216368 H 3.807373 5.547242 1.770999 H 3.998225 3.059957 1.876392 H 4.945503 3.703433 0.526369 H 1.806973 4.279745 2.569702 H 1.305865 5.727863 1.694286 H 0.036141 3.747312 0.962592 H 0.350808 4.053344 1.509859 H 0.470539 5.591926 0.653971 H 2.061598 3.279563 4.181366 H 3.579490 0.247976 3.466185 H 1.918682 0.076320 2.900945 H 2.261557 0.992324 4.374411 H 5.309450 0.572055 1.955187 H 5.737657 0.991913 0.291701 H 3.283783 5.398996 0.662872 H 4.747417 4.177405 0.913496 H 3.282564 3.477985 1.599536 H 4.605438 2.423286 1.099737 H 1.117590 5.956530 3.085787 H 2.683311 6.651749 2.653010 H 2.477468 5.810918 4.200761 N 1.199730 1.975528 0.853611 O 2.196205 2.578777 1.220677 C 0.776826 0.630851 1.777682 H 0.087019 0.343576 2.393145 C 1.940603 1.048400 2.642977 H 2.839035 1.198375 2.045951 H 2.155947 0.280165 3.393231 O 1.734057 2.33 3960 3.288801 C 1.136993 2.476228 4.503686 O 0.910238 3.592207 4.906422 C 0.818026 1.226490 5.306313 H 1.733275 0.685604 5.573611 H 0.171490 0.535983 4.755219 H 0.313257 1.539351 6.220595 C 1.169598 3.523001 0.095754 C 0.998071 2.392331 0.952370 C 1.453567 1.259042 0.965890 C 1.534617 2.751997 1.404414 H 1.977939 4.194706 0.204350 H 2.548518 2.994964 1.735429 C 2.026238 1.356590 0.472432 H 1.998229 0.416138 1.022656 C 0.349620 1.674525 0.665903 C 0.041664 0.990549 0.732736 H 1.100427 2.718644 1.990076 H 1.952117 0.570857 1.651755 H 1.173093 2.379151 0.548858 H 0.65 0605 1.371117 1.547004 H 0.851225 2.968364 2.231606 H 0.256776 4.119829 0.193920 O 3.331224 1.932449 0.562054 C 4.437474 1.181623 0.292015 C 4.423737 0.181297 0.032927 C 5.659457 1.870955 0. 358193 C 5.627530 0.836079 0.291667 H 3.500813 0.742723 0.092069 C 6.851144 1.207686 0.101061 H 5.646983 2.926667 0.609927 C 6.843459 0.153284 0.229904 H 5.607115 1.888409 0.556325 H 7.791261 1.747678 0.145895 C 8.131573 0.884897 0.460448 F 8.598735 1.470399 0.671206 F 9.112929 0.060303 0.898413 F 7.997868 1.873944 1.374412 6E*

PAGE 199

192 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0775645900 0 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2019279100 a.u Ru 0.876948 0.679544 0.236743 O 1.153512 1.216101 0.712381 O 0.516746 1.768565 2.753113 N 3.495049 1.774370 0.281935 N 3.844579 0.370412 0.5 86049 C 2.884878 0.560018 0.285698 C 4.903968 1.744355 0.690031 C 2.674623 2.989831 0.351599 C 2.391717 3.353143 1.835646 C 1.458939 4.575484 1.914104 C 2.129384 5.772510 1.208801 C 2.403872 5.416031 0.266923 C 3.353744 4.198120 0.335608 C 1.069146 5.079177 0.962162 C 0.398230 3.869335 0.259922 C 1.356322 2.673537 0.371277 C 0.130591 4.225974 1.216661 C 3.664972 1.717308 1.063344 C 3.263144 1.903385 2.407895 C 3.109964 3.205191 2.886129 C 3.064019 0.734217 3.348435 C 5.185035 0.236125 0.768051 C 4.019368 2.819001 0.263903 C 3.379083 4.325336 2.087745 C 3.851737 4.107025 0.794259 C 4.596208 2.690358 1.128405 C 3.172482 5.723162 2.621774 H 1.578198 2.480603 1.444506 H 5.537050 2.249917 0.044838 H 5.039988 2.246041 1.656213 H 1.927896 2.490115 2.331381 H 3.335024 3.565272 2.357988 H 1.276368 4.821565 2.968292 H 3.067153 6.035302 1.718731 H 1.478618 6.654937 1.265534 H 2.881928 6.266180 0.770178 H 3.582959 3.946292 1.379621 H 4.304620 4.440 898 0.160778 H 1.233607 4.850088 2.023065 H 0.398252 5.948243 0.923632 H 0.548341 3.651470 0.755028 H 0.357467 3.382712 1.723053 H 0.560919 5.077147 1.271737 H 2.789893 3.351042 3.915656 H 4.016148 0.229021 3.559472 H 2.383550 0.022628 2.948021 H 2.660354 1.076801 4.305701 H 5.611224 0.071890 1.727372 H 5.862100 0.102354 0.024347 H 4.108111 4.960731 0.170460 H 5.514117 3.283991 1.210313 H 3.898898 3.067888 1.885222 H 4.842104 1.657461 1.384312 H 2.113109 6.007681 2.579940 H 3.732990 6.461395 2.039899 H 3.487113 5.803101 3.668292 N 1.429327 1.702862 1.905475 O 2.584682 2.067487 2.108287 C 0.708146 0.779320 1.625465 H 0.220822 0.655282 2.184896 C 1.866955 1.050937 2.551443 H 2.810750 1.059462 2.011534 H 1.915527 0.276774 3.322092 O 1.774492 2.364986 3.153282 C 1.130211 2.592305 4.337457 O 1.017901 3.734618 4.711093 C 0.631168 1.400197 5.133623 H 1.473330 0.801195 5.500672 H 0.013861 0.734808 4.551417 H 0.076834 1.784718 5.990051 C 0.72 1149 3.471866 0.868532 C 0.759985 2.540756 0.372656 C 1.216889 1.136666 1.357609 C 1.112006 2.525513 2.050285 H 1.449288 4.278750 0.752602 H 2.075809 2.810945 2.480635 C 1.861115 1.542786 0. 009401 H 1.966548 0.717998 0.688603 C 0.524329 1.658648 0.368244 C 0.226062 0.759687 0.982045 H 0.903217 3.062681 1.322044 H 1.749677 0.378232 1.936404 H 1.425675 2.245614 0.198708 H 0.922392 1.026677 1.775016 H 0.371113 2.524874 2.856588 H 0.266194 3.927490 0.998482 O 3.101298 2.237555 0.145490 C 4.260343 1.530370 0.292617 C 4.369368 0.135870 0.194096 C 5.402782 2.305611 0.54918 9 C 5.620490 0.461167 0.349296 H 3.511547 0.490728 0.020451 C 6.640667 1.697782 0.704393 H 5.292986 3.382998 0.622202 C 6.757825 0.305528 0.608806 H 5.702377 1.540336 0.269290 H 7.518386 2. 302300 0.908880 C 8.101489 0.349925 0.720510 F 8.712694 0.477777 0.483386 F 8.948039 0.358600 1.506236 F 8.017256 1.596448 1.241745 7E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0775645900 0 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2019279100 a.u Ru 0.214746 1.056538 0.604691

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193 O 0.619054 0.655081 1.875123 O 1.470152 0.068371 1.989094 N 0.550509 3.838249 0.045410 N 2.484080 2.863928 0.444311 C 1.213516 2.650474 0.020939 C 1.332598 4.905795 0.678308 C 0.912923 3.799368 0.050827 C 1.552482 3.763063 1.360405 C 3.079634 3.595852 1.243547 C 3.661759 4.780272 0.446195 C 3.029087 4.81275 3 0.960381 C 1.497176 4.998992 0.831362 C 3.351533 3.486956 1.684611 C 2.752653 2.294965 0.890422 C 1.231808 2.500678 0.821236 C 3.380190 2.269697 0.517948 C 3.578796 1.932168 0.380861 C 4. 059625 1.366279 1.578443 C 5.150496 0.495261 1.512134 C 3.445214 1.699083 2.918790 C 2.748658 4.302482 0.666457 C 4.206736 1.665758 0.850229 C 5.782419 0.184059 0.302403 C 5.297096 0.787946 0.861382 C 3.742795 2.299230 2.142057 C 6.948592 0.774187 0.260448 H 0.872863 2.653508 1.871472 H 1.267345 5.842517 0.117642 H 0.979306 5.091626 1.701578 H 1.120252 2.931709 1.928643 H 1.317956 4.691378 1.900020 H 3.518311 3.576258 2.249808 H 3.466716 5.724552 0.973947 H 4.752280 4.680620 0.363858 H 3.441290 5.654139 1.532107 H 1.029104 5.054990 1.823246 H 1.281702 5.945975 0.314697 H 2.945547 3.501043 2.705234 H 4.440355 3.371324 1.775887 H 2.974527 1.357847 1.415804 H 2.979797 1.427568 1.093794 H 4.465239 2.119338 0.438763 H 5.523828 0.052968 2.433326 H 3.86 3034 1.059907 3.702271 H 3.639657 2.739797 3.211251 H 2.358864 1.565881 2.915824 H 3.291543 4.460507 1.601731 H 3.359170 4.700062 0.154655 H 5.786913 0.579121 1.810053 H 3.479368 3.355256 2. 017841 H 4.529465 2.238536 2.900373 H 2.861348 1.784064 2.538492 H 6.605931 1.814278 0.198002 H 7.585920 0.585450 0.609999 H 7.567957 0.685874 1.159941 N 0.521308 0.855530 2.424303 O 0.724327 1.694201 3.271873 C 2.389377 3.613358 0.114897 H 2.152529 4.635926 0.181324 C 3.443049 3.416474 1.166753 H 3.387609 2.405595 1.574973 H 3.325849 4.123792 1.993688 O 4.788048 3.505985 0.624790 C 5.478684 4.667446 0.527554 O 6.575700 4.641509 0.016752 C 4.859029 5.936324 1.086621 H 4.739331 5.868472 2.174089 H 3.872749 6.137416 0.656377 H 5.529280 6.764956 0.856951 C 1.0031 91 1.923344 2.806462 C 0.660726 2.688609 1.486693 C 0.779203 0.687941 1.718828 C 0.239390 1.068538 3.119643 H 1.265470 2.609346 3.617693 H 0.991352 1.666390 3.645921 C 0.665771 2.046347 0.97 9355 H 0.696790 1.963929 0.105827 C 1.750710 2.587625 0.456539 C 0.009280 0.482866 1.127494 H 0.449798 3.742818 1.692155 H 1.836667 0.390853 1.764085 H 2.021788 1.576265 0.150816 H 0.522339 1.033568 1.928827 H 0.014967 0.193629 3.740181 H 1.873665 1.276710 2.640754 O 1.717443 2.927087 1.427187 C 2.984754 2.788312 0.947373 C 3.355309 1.969791 0.129698 C 3.961740 3.556959 1.603188 C 4.689180 1.933292 0.537231 H 2.623946 1.375210 0.662394 C 5.284944 3.511102 1.189002 H 3.655501 4.180640 2.436957 C 5.660419 2.693203 0.115146 H 4.971717 1.298061 1.370643 H 6.034038 4.10 2122 1.706191 C 7.081729 2.682803 0.362460 F 7.326359 3.662876 1.266994 F 7.957189 2.872211 0.653341 F 7.407172 1.514097 0.963203 8E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0775645900 0 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.2019279100 a.u Ru 0.077784 1.356547 0.709374 O 1.489497 0.149769 1.809571 O 0.543693 0.299799 2.554789 N 1.341782 3.739089 0.301049

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194 N 2.962270 2.301616 0.0 71387 C 1.618910 2.482294 0.137759 C 2.514148 4.419002 0.860811 C 0.054598 4.066915 0.604457 C 0.364663 3.819563 2.102460 C 1.863927 4.052401 2.374836 C 2.228726 5.504129 2.007536 C 1.924641 5.747758 0.514505 C 0.413895 5.529114 0.256367 C 2.760353 4.766074 0.337203 C 2.385218 3.303546 0.023943 C 0.890702 3.117887 0.278444 C 2.687059 3.069750 1.518141 C 3.720228 1.215081 0.627065 C 4.330096 0.296986 0.249608 C 5.116107 0.724815 0.293770 C 4.178937 0.399340 1.750116 C 3.662716 3.539278 0.336568 C 3.918035 1.133738 2.019611 C 5.321198 0.841633 1.672692 C 4.714147 0.0 95571 2.514317 C 3.297105 2.121236 2.980556 C 6.203662 1.934846 2.230047 H 0.725035 3.437145 1.338881 H 2.584426 5.454693 0.516382 H 2.472608 4.424642 1.958417 H 0.084151 2.791681 2.358336 H 0.238480 4.494932 2.725475 H 2.068012 3.877991 3.439442 H 1.659429 6.207814 2.631126 H 3.292655 5.688182 2.207823 H 2.184352 6.780263 0.247522 H 0.168439 5.727518 0.795546 H 0.171085 6.232574 0.867162 H 2.585792 4.945665 1.406726 H 3.830462 4.936853 0.155658 H 2.973745 2.610588 0.589534 H 2.447227 2.037724 1.796241 H 3.759628 3.213635 1.706890 H 5.564480 1.455609 0.374538 H 4.377224 0.567252 2.222697 H 4.891295 1.119011 2.177392 H 3.176656 0.727921 2.040460 H 4.422133 3.326717 1.093363 H 4.161941 3.986231 0.533192 H 4.865770 0.023390 3.589356 H 3.284218 3.140471 2.580237 H 3.853079 2.137690 3.923197 H 2.262542 1.844488 3.211710 H 6.215087 2.808310 1.570346 H 5.869587 2.253455 3.223423 H 7.241657 1.590586 2.331145 N 0.657770 0.182233 2.729339 O 0.94 4486 0.874357 3.677944 C 2.184112 3.869375 0.751558 H 1.846399 4.787095 1.234357 C 3.407861 3.952700 0.112890 H 3.496694 3.057575 0.731045 H 3.374157 4.824245 0.774725 O 4.639799 3.967463 0. 657303 C 5.201487 5.108123 1.141385 O 6.195195 5.014212 1.821784 C 4.571106 6.441252 0.777277 H 4.641029 6.627818 0.300679 H 3.513365 6.489402 1.054581 H 5.118053 7.222687 1.305344 C 0.411937 1.714308 3.040467 C 0.252025 2.617268 1.769891 C 0.979377 0.490716 1.452416 C 0.728770 0.672109 2.972329 H 0.375468 2.308752 3.958341 H 1.634501 1.064660 3.445259 C 0.918160 1.971747 0.97632 2 H 0.819325 2.081057 0.107416 C 1.502964 2.734721 0.944180 C 0.091422 0.426389 0.868649 H 0.072465 3.621622 2.057389 H 1.975067 0.094317 1.227977 H 1.860918 1.820456 0.466925 H 0.977436 0. 491098 1.515455 H 0.471596 0.268085 3.472529 H 1.390182 1.220519 3.027625 O 2.083529 2.678933 1.440568 C 3.288477 2.608655 0.804866 C 3.525837 1.963558 0.413984 C 4.339368 3.272620 1.461483 C 4.807589 1.996281 0.967027 H 2.743063 1.430112 0.937661 C 5.608314 3.295967 0.902913 H 4.132629 3.762189 2.407861 C 5.852450 2.654906 0.319469 H 4.987453 1.492294 1.910909 H 6.416895 3.804814 1.418378 C 7.215659 2.730871 0.939176 F 7.410519 3.897203 1.603707 F 8.196931 2.657055 0.007158 F 7.429489 1.736169 1.829908 9E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0775645900 0 a.u. M06/SD D/6 311++G(d,p) SCF energy in solution: 2562.2019279100 a.u Ru 1.816660 0.707973 0.735373 O 0.261185 2.084388 1.630845 O 0.673429 0.129771 2.486295 N 4.472118 0.142626 0.013547 N 3.294252 1.979503 0.284801 C 3.238474 0.623775 0.329828 C 5.391554 1.191015 0.440100

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195 C 4.582155 1.281849 0.317381 C 4.444149 1.504275 1.845945 C 4.428778 3.012827 2.159538 C 5.745684 3.646874 1.668163 C 5.884017 3.42 7696 0.147111 C 5.913480 1.909391 0.154656 C 4.687021 4.095714 0.565723 C 3.360170 3.450860 0.082258 C 3.417238 1.957905 0.434992 C 3.228497 3.660399 1.440026 C 2.291082 2.903012 0.737447 C 1.588626 3.660037 0.220503 C 0.653424 4.600322 0.225164 C 1.832790 3.496810 1.703156 C 4.669828 2.463447 0.036456 C 2.084891 3.102325 2.116307 C 0.417547 4.814999 1.587673 C 1.141339 4.056389 2.512362 C 2.838039 2.316958 3.164806 C 0.569103 5.865520 2.043776 H 3.654070 1.883787 1.526386 H 6.385471 1.077883 0.002225 H 5.497742 1.169003 1.533171 H 3.519633 1.030475 2.194654 H 5.28 1964 1.022570 2.369586 H 4.332350 3.154351 3.244144 H 6.600587 3.201666 2.196524 H 5.755442 4.721585 1.894022 H 6.820721 3.877146 0.207163 H 6.042464 1.732083 1.230737 H 6.769933 1.447116 0. 358127 H 4.782251 3.986661 1.654702 H 4.684725 5.173687 0.352423 H 2.513467 3.918996 0.598979 H 2.292133 3.220046 1.802511 H 3.189982 4.735017 1.665339 H 0.087079 5.168321 0.508903 H 1.024085 3.957136 2.278247 H 2.768321 3.981430 2.015084 H 1.906541 2.444022 1.992893 H 4.674604 3.264903 0.706532 H 5.098304 2.857280 0.967597 H 0.974420 4.212051 3.576275 H 3.877096 2.126333 2.876611 H 2.846433 2.858654 4.115857 H 2.361113 1.346473 3.340433 H 1.331679 6.051544 1.280679 H 1.070576 5.569374 2.971666 H 0.064808 6.821417 2.238885 N 0.007850 1.248578 2.562589 O 0.81015 4 1.449091 3.443745 C 2.943052 2.321195 1.086389 H 3.876404 2.102961 1.606594 C 2.874269 3.585831 0.278932 H 2.039458 3.538682 0.422584 H 3.793604 3.746188 0.293465 O 2.583274 4.758851 1.083 575 C 3.547772 5.496517 1.698507 O 3.205388 6.423154 2.393292 C 5.003284 5.136565 1.456140 H 5.277338 5.291360 0.406030 H 5.218756 4.092820 1.705494 H 5.615481 5.789592 2.078517 C 0.965843 0.131175 3.153987 C 1.933631 0.160450 1.924507 C 0.038150 1.392674 1.502723 C 0.167063 1.182530 3.030769 H 1.514686 0.205596 4.097832 H 0.731264 2.016254 3.462929 C 1.460279 1.020497 1.014757 H 1.481652 0.780304 0.051160 C 1.917618 1.466937 1.180802 C 1.061315 0.514403 0.918081 H 2.957335 0.048792 2.251214 H 0.139746 2.437366 1.229170 H 0.986498 1.711627 0.665004 H 1.356658 0.313 586 1.577765 H 0.803370 1.137205 3.537931 H 0.291408 0.994743 3.115994 O 2.259064 2.193387 1.247742 C 3.496061 2.300293 0.691472 C 4.117551 1.311446 0.084524 C 4.164193 3.512163 0.936908 C 5.389755 1.545190 0.607786 H 3.629198 0.364647 0.281511 C 5.429841 3.731373 0.414453 H 3.663074 4.267926 1.532976 C 6.053309 2.747481 0.364878 H 5.863772 0.782104 1.216562 H 5.935194 4.673622 0.600360 C 7.446046 2.964228 0.876628 F 8.385761 2.588849 0.028262 F 7.684755 4.266239 1.157213 F 7.691122 2.254446 2.002046 TS15* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0444131100 a.u. M06/SDD/6 311++ G(d,p) SCF energy in solution: 2562.1796358200 a.u Ru 1.181826 0.517628 0.184734 O 1.395344 1.205139 2.366738 O 0.316717 1.812519 1.183259 N 3.892111 0.571374 0.836295 N 3.401896 1.562905 0.760298 C 2.9 16592 0.309201 0.484726 C 5.161575 0.065040 1.199530 C 3.800017 1.969848 0.398408 C 4.497512 2.149942 0.975595 C 4.346394 3.605736 1.461338

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196 C 4.966618 4.564901 0.426945 C 4.244851 4.389890 0 .924596 C 4.448779 2.937899 1.416130 C 2.740097 4.690714 0.743087 C 2.119429 3.703489 0.285084 C 2.297449 2.281976 0.299899 C 2.847437 3.915431 1.631973 C 2.909659 2.840511 0.336607 C 3.135151 3.248470 0.996365 C 2.707153 4.520229 1.384684 C 3.862052 2.358774 1.980277 C 4.733784 1.521950 1.404250 C 2.335891 3.720680 1.272174 C 2.088812 5.402019 0.488779 C 1.924626 4.986764 0.834441 C 2.176060 3.346308 2.728180 C 1.613511 6.760968 0.947634 H 1.931829 2.344845 1.335875 H 5.584942 0.379425 2.104068 H 5.896715 0.041037 0.390332 H 4.045264 1.463430 1.700541 H 5.56392 2 1.895475 0.891830 H 4.860845 3.717115 2.424878 H 6.041465 4.363695 0.311444 H 4.870990 5.602712 0.773136 H 4.672336 5.078861 1.665136 H 3.988441 2.792613 2.403123 H 5.525586 2.738804 1.524 681 H 2.219604 4.611581 1.707887 H 2.611495 5.725928 0.396743 H 1.053278 3.928094 0.399724 H 2.429246 3.282742 2.416881 H 2.716255 4.958002 1.953719 H 2.873976 4.837488 2.412053 H 4.884040 2.144060 1.642104 H 3.366888 1.391881 2.119388 H 3.933720 2.844272 2.957918 H 5.409333 2.240642 0.931901 H 4.646762 1.781735 2.466883 H 1.466859 5.664531 1.551931 H 3.053505 3.652931 3.313625 H 1.306924 3.845142 3.168680 H 2.058392 2.267362 2.861430 H 0.668442 6.683386 1.500606 H 1.444554 7.433761 0.101048 H 2.340475 7.233562 1.617649 N 0.295794 1.866818 2.319217 O 0.135989 2.501 844 3.262576 C 0.295389 0.090139 1.427134 H 0.637086 0.616687 2.195706 C 0.918057 0.855738 1.883220 H 0.573618 1.679943 2.524372 H 1.465008 1.306232 1.053591 O 1.887143 0.040505 2.582907 C 1.829314 0.201300 3.924170 O 2.564909 1.037938 4.388342 C 0.871411 0.622839 4.766481 H 0.168511 0.506970 4.443328 H 1.118632 1.689530 4.714673 H 0.966064 0.286436 5.799155 C 1.825387 3.071314 1.000911 C 1.668544 1.757123 0.161082 C 0.916994 1.157675 2.220680 C 1.330142 2.654511 2.420974 H 2.877534 3.369136 1.018744 H 2.136513 2.725400 3.155412 C 2.009764 0.694948 1.233298 H 1.883 657 0.335844 0.906522 C 0.158756 1.588268 0.039838 C 0.317437 1.234917 1.326928 H 2.231132 1.742623 0.771009 H 0.822197 0.582606 3.143012 H 0.399282 2.240320 0.617270 H 1.222424 1.666113 1.735830 H 0.490339 3.259873 2.775867 H 1.249604 3.895833 0.568989 O 3.288542 0.847048 1.849194 C 4.403909 0.332001 1.258174 C 4.472177 0.133412 0.061796 C 5.550051 0.296143 2.069248 C 5.6794 59 0.631617 0.552633 H 3.614355 0.093411 0.721032 C 6.745707 0.198878 1.569237 H 5.472642 0.653009 3.091159 C 6.818069 0.671243 0.252201 H 5.728333 0.990737 1.575432 H 7.624462 0.233388 2.20 5140 C 8.124364 1.153717 0.304327 F 8.861213 0.143002 0.829593 F 8.894664 1.734881 0.645449 F 7.951861 2.059110 1.295107 TS16* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0270513900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1617292200 a.u Ru 1.855147 0.350670 0.174139 O 1.615826 0.277367 2.452603 O 1.757768 2.171398 1.408460 N 3.582213 1.921564 0.346479 N 1.681372 2.513811 1.252032 C 2.302684 1.508773 0.552009 C 3.829534 3.311025 0.742196 C 4.450370 1.192469 0.584741 C 4.339020 1.785221 2.014370 C 5.215361 0.975805 2.992896 C 6.682836 1.005738 2.524397 C 6.778005 0.391331 1.113277 C 5.931977 1.243019 0.140162

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197 C 6.252150 1.061355 1.147467 C 4.765236 1.078479 1.602297 C 3.966698 0.267589 0.552178 C 4.711693 0.479281 3.026222 C 0.300189 2.684658 1.594590 C 0.561783 3.2 79625 0.645473 C 1.897178 3.487083 0.994864 C 0.054968 3.716741 0.711192 C 2.611296 3.602992 1.620752 C 0.154246 2.387327 2.891342 C 2.394795 3.147084 2.261036 C 1.505091 2.613386 3.194112 C 0.767026 1.860054 3.968544 C 3.852507 3.359930 2.597675 H 4.278855 0.666509 0.423534 H 4.772995 3.409221 1.285009 H 3.872047 3.965459 0.139344 H 3.291819 1.757113 2.336268 H 4.660833 2.836749 2.010523 H 5.136997 1.418914 3.994353 H 7.064152 2.037105 2.513948 H 7.311449 0.439896 3.225027 H 7.822858 0.397588 0.775438 H 6.017853 0.861340 0.886350 H 6.311481 2.275827 0.139071 H 6.3 51866 1.522224 0.154750 H 6.864309 1.657793 1.838767 H 4.406741 2.113891 1.622820 H 3.703850 0.507361 3.441301 H 5.349038 1.077242 3.692620 H 2.566469 3.937650 0.264586 H 0.707803 4.500473 0 .618710 H 0.404477 2.897252 1.274542 H 0.871808 4.123482 1.314646 H 2.159013 4.579088 1.424416 H 2.849379 3.546406 2.691191 H 1.865250 2.365555 4.190497 H 1.068591 2.665852 4.651087 H 0.267769 1.097814 4.576220 H 1.677409 1.422297 3.552920 H 4.494353 2.672367 2.032190 H 4.046131 3.193921 3.661712 H 4.175469 4.377971 2.349845 N 1.647599 1.557132 2.537996 O 1.573973 2.153239 3.597499 C 1.797242 1.099546 1.558755 H 1.726409 0.557224 2.509194 C 2.029684 2.559525 1.815307 H 3.082448 2.649777 2.135416 H 1.896135 3.171895 0.920972 O 1.163790 2.998948 2.883957 C 1.1593 74 4.290587 3.325220 O 0.408250 4.588410 4.221759 C 2.098915 5.273222 2.653245 H 3.141165 4.940505 2.710933 H 1.852233 5.393683 1.592279 H 1.998293 6.235704 3.155161 C 1.305053 2.287538 1.29 1433 C 1.572808 0.790453 1.015484 C 1.372304 1.674247 1.074360 C 1.076028 2.870461 0.131530 H 2.201514 2.719995 1.746278 H 1.774536 3.683281 0.349316 C 2.477315 0.922457 0.267746 H 2.735728 0.043542 0.714451 C 0.433166 0.023482 0.325249 C 0.343450 0.543193 0.986916 H 2.001045 0.253084 1.864741 H 1.628904 1.959640 2.095445 H 0.364981 1.037884 0.515768 H 0.220030 0.102894 1.843516 H 0.065152 3.254828 0.259204 H 0.475918 2.469823 1.968039 O 3.650374 1.715868 0.140765 C 4.813290 1.139300 0.273837 C 4.922105 0.165932 0.775073 C 5.960098 1.943315 0.175686 C 6.169879 0.653330 1.163517 H 4.048410 0.798059 0.877647 C 7.195872 1.449453 0.569489 H 5.855634 2.948800 0.218710 C 7.310670 0.143541 1.063190 H 6.251814 1.665014 1.547900 H 8.079098 2.073888 0.483229 C 8.634928 0.375018 1.541368 F 8.830912 0.132984 2.860366 F 9.670100 0.197026 0.885037 F 8.740675 1.714815 1.376393 TS17* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0284788100 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 2562.1679958300 a.u Ru 1.832873 0.322474 0.509158 O 3.347281 0.546380 2.032539 O 2.817287 1.556576 2.073903 N 2.344514 0.945791 2.049699 N 0.555569 1.995080 1.335428 C 1.465058 1.018633 1.010047 C 2.040700 1.838330 3.169687 C 3.679938 0.384162 1.833514 C 4.642850 1.513706 1.373738 C 6.033076 0.935391 1.051448 C 6.602775 0.233704 2.300175 C 5.646913 0.896925 2.730657 C 4.270639 0.287947 3.094972 C 5.506347 1.903508 1.566806 C 4.907497 1.194143 0.319335 C 3.514749 0.675067 0.742820

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198 C 5.878293 0.071078 0.104075 C 0.309207 2.763633 0.483821 C 0.2458 66 3.612531 0.498896 C 0.612546 4.468015 1.197432 C 1.725459 3.634723 0.801302 C 0.894014 2.681596 2.607748 C 1.682140 2.821181 0.791826 C 1.988575 4.512841 0.947196 C 2.499865 3.684413 0.05 4160 C 2.285145 2.010494 1.916558 C 2.894720 5.419790 1.746372 H 3.017183 1.531137 1.226354 H 1.740084 1.257760 4.050104 H 2.909761 2.442877 3.446161 H 4.224522 1.997507 0.483406 H 4.726346 2.278090 2.159969 H 6.701398 1.751731 0.747242 H 6.731359 0.955688 3.119407 H 7.596394 0.178988 2.079910 H 6.052462 1.408194 3.613602 H 3.584078 1.067443 3.452456 H 4.396098 0.437163 3.912853 H 4.867454 2.745657 1.867549 H 6.492796 2.323613 1.324631 H 4.806040 1.923836 0.491080 H 5.512059 0.443137 0.996927 H 6.854370 0.507488 0.357175 H 0.188669 5.124550 1.954545 H 2.328547 3.71 5711 0.110673 H 2.049397 2.723643 1.315397 H 1.971738 4.488370 1.440006 H 1.191812 3.715777 2.394241 H 0.026413 2.711265 3.271107 H 3.563990 3.712092 0.278259 H 2.264557 2.569866 2.862146 H 3.331681 1.771549 1.709761 H 1.746096 1.073188 2.081915 H 3.280061 4.906358 2.637271 H 3.760105 5.742340 1.157806 H 2.364602 6.314099 2.090813 N 3.532087 0.600585 2.575783 O 4.316702 0.788157 3.485056 C 0.554148 1.587982 0.073693 H 0.377718 1.367029 0.608114 C 0.831134 3.063671 0.038317 H 1.257026 3.330173 1.021106 H 1.565653 3.324320 0.729357 O 0.403329 3.785139 0.159919 C 0.437245 5.142491 0.303773 O 1.507743 5.674271 0.468514 C 0.878453 5.894418 0.254443 H 1.422994 5.697783 0.675718 H 1.531534 5.602294 1.084882 H 0.662282 6.960301 0.328895 C 1.582204 0.484631 3.699048 C 0.964944 0.973919 2.344601 C 1.514253 1.188690 1.914197 C 1.942598 1.002704 3.406054 H 2.477158 1.067902 3.933708 H 3.017702 1.178953 3.503954 C 1.841672 0.203668 1.337526 H 1.52 4443 0.336141 0.301606 C 0.359575 0.225621 2.245862 C 0.009036 1.125859 1.949285 H 0.936027 2.054496 2.231463 H 1.938594 2.065109 1.427102 H 1.134800 0.463899 2.967058 H 0.553530 1.956691 2. 385093 H 1.428547 1.711579 4.062330 H 0.875610 0.600041 4.526540 O 3.201686 0.615011 1.480630 C 4.167412 0.118686 0.660707 C 3.975394 0.879486 0.304745 C 5.444175 0.682980 0.829109 C 5.050289 1.294714 1.092432 H 3.008087 1.346200 0.441914 C 6.505348 0.262032 0.041619 H 5.574924 1.448282 1.587405 C 6.315151 0.731042 0.929146 H 4.898627 2.074856 1.830916 H 7.489301 0.698187 0.182920 C 7.456683 1.133211 1.815349 F 7.632992 0.260571 2.839825 F 8.629071 1.168583 1.139813 F 7.269387 2.351032 2.370237 TS18* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0062711000 a.u. M06/SDD/6 311++G(d ,p) SCF energy in solution: 2562.1496818100 a.u Ru 1.784810 0.555650 0.148688 O 0.878199 3.949111 0.048195 O 1.531065 2.398703 1.381759 N 3.584107 0.776926 1.611127 N 2.265205 2.442692 1.060711 C 2.4885 36 1.092778 0.874854 C 4.030836 1.843936 2.507665 C 4.271917 0.499486 1.367323 C 3.838113 1.600267 2.367516 C 4.520409 2.936925 2.005445 C 6.051435 2.765934 2.052090 C 6.473152 1.679331 1.04 2298 C 5.809299 0.342952 1.444663 C 6.031689 2.088708 0.379754 C 4.489959 2.255270 0.427309 C 3.867498 0.887877 0.080325 C 4.088087 3.348865 0.585422 C 1.575678 3.361735 0.191418 C 0.535229 4.159191 0.704802

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199 C 0.094202 5.074562 0.149737 C 0.099205 4.115640 2.152060 C 3.322265 3.057675 1.902169 C 2.063102 3.586011 1.119128 C 0.298029 5.244843 1.476821 C 1.397079 4.505980 1.931646 C 3.311086 2.909862 1.642807 C 0.428342 6.199359 2.394115 H 4.303689 0.129496 0.747762 H 5.117544 1.946628 2.506296 H 3.705310 1.645297 3.537916 H 2.744248 1.717442 2.339806 H 4.098720 1.29 3879 3.391100 H 4.209749 3.704236 2.726031 H 6.380246 2.490185 3.064422 H 6.539381 3.718108 1.805821 H 7.563240 1.551376 1.069224 H 6.131969 0.463771 0.772287 H 6.127796 0.074760 2.462681 H 6.357542 1.332901 1.108209 H 6.520463 3.032486 0.658730 H 4.179836 2.556066 1.433575 H 3.010549 3.527378 0.558277 H 4.574042 4.295987 0.312957 H 0.913399 5.672763 0.244355 H 0.524292 3.269401 2.691482 H 0.991113 4.051126 2.232651 H 0.404209 5.035904 2.667676 H 2.881408 3.716223 2.654274 H 3.992382 3.658453 1.273083 H 1.760676 4.665686 2.944470 H 4.170280 3.084787 0.983630 H 3.56 9806 3.305346 2.629499 H 3.195179 1.825780 1.730470 H 1.183886 5.671363 2.990462 H 0.259511 6.681421 3.097336 H 0.945214 6.982975 1.830773 N 0.990316 3.563011 1.132172 O 0.621027 4.233868 2. 099756 C 1.097186 0.366011 1.612714 H 0.763500 1.403040 1.512072 C 0.996781 0.139444 3.030753 H 1.692515 0.453104 3.646240 H 1.260816 1.190192 3.102065 O 0.343122 0.115415 3.505932 C 1.014416 0.768990 4.307378 O 2.169496 0.526196 4.563768 C 0.274971 1.988849 4.819313 H 0.658212 1.713003 5.322910 H 0.020325 2.682657 4.007734 H 0.930216 2.497790 5.526961 C 1.513990 1.399678 0.557736 C 1.921166 0.073579 0.127304 C 1.063622 0.594071 1.874491 C 0.920528 0.941273 1.925257 H 2.402679 2.021176 0.701381 H 1.495166 1.347167 2.762707 C 2.416164 0.748814 1.118977 H 2.6509 65 1.793148 0.884260 C 0.718245 0.800746 0.438531 C 0.165805 1.204588 0.795498 H 2.612155 0.191288 0.963309 H 1.003534 1.093122 2.844215 H 0.682278 1.401038 1.336247 H 0.231980 2.212926 0.92 4552 H 0.123043 1.226967 2.046943 H 0.808273 1.961833 0.051847 O 3.478682 0.166125 1.858106 C 4.772859 0.377445 1.475840 C 5.161665 1.024038 0.295826 C 5.749423 0.105987 2.360999 C 6.518963 1.183723 0.013527 H 4.427217 1.397170 0.407532 C 7.095936 0.056046 2.069324 H 5.425923 0.596994 3.273094 C 7.490635 0.705301 0.891929 H 6.817162 1.688355 0.899342 H 7.846848 0.310933 2.761752 C 8.949119 0.826922 0.560080 F 9.431848 0.295663 0.027137 F 9.699927 1.031836 1.668075 F 9.194431 1.847795 0.291113 TS19* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0062218200 a.u. M06/SDD/6 311++G(d,p) SCF e nergy in solution: 2562.1495019900 a.u Ru 1.596649 0.588256 0.327667 O 0.022473 3.227689 2.091898 O 1.583479 1.678269 2.277782 N 2.585018 0.714475 2.332997 N 2.048274 1.411005 2.212614 C 2.054388 0.2 23371 1.508136 C 2.758367 0.266790 3.715377 C 3.031550 1.996383 1.768043 C 1.962388 3.107361 1.920821 C 2.446401 4.400038 1.231078 C 3.770525 4.861856 1.870610 C 4.831825 3.756063 1.699626 C 4.343724 2.482761 2.426850 C 5.045013 3.464289 0.197882 C 3.713380 2.994334 0.443694 C 3.292530 1.691746 0.267237 C 2.665754 4.114141 0.267162 C 2.068762 2.754864 1.692991 C 1.101794 3.682863 2.123971 C 1.165838 4.995131 1.636134 C 0.029156 3.345261 3.134648 C 2.674454 1.252886 3.549296

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200 C 3.159843 3.181700 0.897252 C 2.173253 5.418769 0.770411 C 3.174870 4.499486 0.435320 C 4.329724 2.277122 0.579004 C 2.194241 6.823789 0.217469 H 4.136152 0.986121 0.227162 H 3.713127 0.593499 4.131543 H 1.953734 0.658266 4.352592 H 1.012962 2.776666 1.473236 H 1.764824 3.285204 2.988065 H 1.683038 5.179101 1.353145 H 3.627223 5.086363 2.937380 H 4.112030 5.788778 1.391709 H 5.778788 4.077620 2.152531 H 5.102447 1.690648 2.365141 H 4.188883 2.712687 3.491311 H 5.822 444 2.698172 0.068853 H 5.405003 4.372080 0.306015 H 3.862928 2.798450 1.510703 H 1.720013 3.838626 0.740741 H 3.017213 5.026480 0.768781 H 0.403299 5.704184 1.952231 H 0.058458 2.272781 3.3 06796 H 0.948845 3.715368 2.809228 H 0.249063 3.826770 4.096874 H 2.066496 1.734483 4.318903 H 3.664814 1.727110 3.551349 H 4.004430 4.823490 0.189543 H 4.739176 1.811217 1.483154 H 5.134612 2.851206 0.110519 H 4.055378 1.462687 0.098076 H 1.770465 6.852553 0.794778 H 3.215966 7.213735 0.151216 H 1.607574 7.508411 0.838371 N 0.743951 2.519540 2.822580 O 0.718703 2.577127 4.054942 C 1.865153 0.958725 1.326696 H 1.740766 1.946547 0.873417 C 2.331239 1.032441 2.758460 H 3.357747 1.434430 2.753826 H 2.334261 0.053303 3.228519 O 1.486249 1.970166 3.458983 C 1.168433 1.8 14861 4.782133 O 0.421223 2.623303 5.278020 C 1.764115 0.642695 5.536259 H 2.857853 0.634978 5.469871 H 1.403827 0.318471 5.148333 H 1.467501 0.738571 6.581161 C 1.198628 2.073940 0.124762 C 1.514250 1.336304 1.199020 C 1.800214 0.268669 0.391230 C 1.407924 0.975870 1.212861 H 1.902424 2.900445 0.256397 H 2.217910 1.246884 1.896809 C 2.665638 0.388422 0.739756 H 2.967677 0.318460 1.520395 C 0.497378 0.244686 1.494778 C 0.651104 0.744008 0.500402 H 1.731332 1.989762 2.045181 H 2.271763 1.064836 0.971613 H 0.172808 0.040404 2.505347 H 0.557134 1.803208 0.747900 H 0.5 10615 0.784364 1.799225 H 0.191167 2.486603 0.118055 O 3.786293 1.143584 0.304107 C 4.975589 0.522136 0.055492 C 5.180076 0.862452 0.100700 C 6.042797 1.374443 0.272899 C 6.446311 1.381437 0 .176205 H 4.370411 1.540981 0.340606 C 7.294782 0.847706 0.551061 H 5.862072 2.444049 0.302351 C 7.505744 0.537519 0.504275 H 6.601543 2.454437 0.144131 H 8.114385 1.510710 0.810512 C 8.878257 1.082281 0.770730 F 9.720377 0.865055 0.268343 F 9.447392 0.494149 1.850535 F 8.865964 2.414725 0.996140 TS15E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0423985800 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 2562.1798292700 a.u Ru 1.013587 0.609504 0.237602 O 1.431658 1.285781 2.379335 O 0.417535 1.858332 1.400854 N 3.654872 0.738323 0.945363 N 3.272625 1.414187 0.693282 C 2.734835 0.159150 0.500089 C 4.939385 0.143076 1.323223 C 3.519581 2.153494 0.566742 C 4.274651 2.424917 0.761576 C 4.076239 3.891915 1.192987 C 4.597553 4.833128 0.089886 C 3.820819 4.565845 1.2152 82 C 4.071883 3.103939 1.654857 C 2.313886 4.806483 0.969707 C 1.792470 3.837309 0.128089 C 2.010431 2.402165 0.407720 C 2.573890 4.138954 1.426422 C 2.927221 2.635379 0.016933 C 3.257758 2 .772241 1.350656 C 2.985259 3.986559 1.985850 C 3.915619 1.650957 2.123457 C 4.616120 1.357282 1.317431 C 2.404814 3.723864 0.739816 C 2.425517 5.073182 1.303325 C 2.158986 4.923798 0.058917

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201 C 2.082086 3.642786 2.215715 C 2.124702 6.367426 2.022524 H 1.601887 2.411142 1.427252 H 5.264632 0.497476 2.305847 H 5.718997 0.403179 0.595961 H 3.892628 1.752931 1.537734 H 5.347492 2.2190 90 0.636218 H 4.630894 4.069392 2.123793 H 5.674203 4.677826 0.071208 H 4.468308 5.879497 0.397283 H 4.178909 5.240260 2.004468 H 3.572740 2.895511 2.611242 H 5.150814 2.949725 1.808405 H 1 .750056 4.662089 1.901805 H 2.155040 5.849282 0.660508 H 0.723024 4.013705 0.288101 H 2.226638 3.523598 2.258368 H 2.409082 5.187071 1.712857 H 3.234050 4.092154 3.039776 H 4.853595 1.331814 1.652197 H 3.277332 0.763579 2.194792 H 4.152140 1.974922 3.141100 H 5.330415 1.946623 0.734844 H 4.583132 1.777321 2.330052 H 1.752597 5.765197 0.616310 H 2.157823 4.631476 2.679056 H 1.0566 37 3.289502 2.386163 H 2.752924 2.966718 2.752521 H 1.174019 6.304770 2.568009 H 2.045954 7.206008 1.323365 H 2.901969 6.607682 2.756266 N 0.306948 1.907151 2.464764 O 0.040612 2.500263 3.468360 C 0.009420 0.210141 1.288349 C 1.943549 3.018441 1.134571 C 1.757666 1.730861 0.261137 C 1.062165 1.070860 2.321575 C 1.479421 2.562060 2.553165 H 2.997444 3.310436 1.136676 H 2.3011 77 2.614583 3.272198 C 2.123309 0.634181 1.290895 H 1.977398 0.385976 0.939660 C 0.246904 1.561666 0.178818 C 0.190685 1.163544 1.456105 H 2.293481 1.744052 0.688092 H 0.992716 0.468753 3.22 8778 H 0.339338 2.188564 0.477554 H 1.115659 1.522918 1.888867 H 0.646777 3.156237 2.941990 H 1.363168 3.858379 0.740649 O 3.424224 0.766285 1.861619 C 4.508986 0.256342 1.215223 C 4.488117 0.315627 0.063735 C 5.720351 0.330888 1.922930 C 5.670043 0.806527 0.619515 H 3.568062 0.379669 0.631556 C 6.889560 0.158302 1.360440 H 5.713556 0.768462 2.915951 C 6.872763 0.733353 0.082354 H 5.649117 1.252353 1.608447 H 7.819745 0.106702 1.917322 C 8.152466 1.208579 0.538660 F 8.844584 0.196441 1.118951 F 8.981888 1.760698 0.378203 F 7.939840 2.134137 1.501836 C 0.325978 0.35 6766 2.630724 H 1.254763 0.932095 2.620256 H 0.462290 0.506148 3.302237 O 0.758021 1.190506 3.097651 C 0.881652 1.565420 4.405417 O 1.774298 2.319050 4.705017 C 0.107224 0.996513 5.405797 H 1.144007 1.191260 5.111259 H 0.010713 0.089266 5.500597 H 0.089162 1.458730 6.373414 H 1.056677 0.551895 1.267118 TS16E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0255982300 a.u. M06/SDD/6 311++G(d,p) SCF energ y in solution: 2562.1621398500 a.u Ru 1.776704 0.524615 0.503996 O 1.501300 2.608238 0.374625 O 1.486651 2.306677 1.773408 N 3.710546 0.632026 1.325691 N 1.825687 1.636773 1.842989 C 2.391185 0.700594 1.002437 C 4.086186 1.419107 2.503448 C 4.515881 0.498878 0.842019 C 4.475540 1.663615 1.866774 C 5.268517 2.871486 1.327618 C 6.728480 2.457763 1.060635 C 6.750346 1.317060 0.023145 C 5.991008 0.100084 0.602628 C 6.079614 1.802940 1.281886 C 4.600406 2.194623 1.006698 C 3.890831 0.915890 0.499875 C 4.610382 3.349697 0.019843 C 0.439055 1.809678 2.181275 C 0.176929 0.859 516 3.027723 C 1.511735 1.054420 3.392209 C 0.576206 0.345051 3.548159 C 2.813913 2.235368 2.769945 C 0.252478 2.969581 1.786012 C 2.243363 2.170127 2.966772 C 1.588070 3.121326 2.182400 C 0.381639 4.052415 0.940668 C 3.696907 2.335824 3.344608 H 4.175784 0.131029 1.213034

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202 H 4.952971 2.052736 2.292857 H 4.344499 0.764681 3.345428 H 3.433835 1.951282 2.045842 H 4.903978 1.338386 2.825804 H 5.242396 3.677613 2.072542 H 7.212786 2.132207 1.992766 H 7.300183 3.317745 0.686739 H 7.788135 1.022727 0.182547 H 6.031664 0.749279 0.093197 H 6.475345 0.218819 1.538022 H 6.127 986 1.017200 2.048566 H 6.632261 2.667080 1.677077 H 4.134884 2.529743 1.940072 H 3.603445 3.714612 0.229621 H 5.177167 4.195405 0.393964 H 1.989901 0.319775 4.036743 H 1.496544 0.054411 4.0 69036 H 0.869951 1.032418 2.746551 H 0.041143 0.904892 4.256696 H 2.462551 2.155396 3.803230 H 2.948820 3.300756 2.546390 H 2.125707 4.014118 1.869567 H 0.012696 5.034851 1.219779 H 0.162301 3.914191 0.126162 H 1.468459 4.080869 1.050180 H 4.351140 1.812604 2.634406 H 3.994476 3.389358 3.343735 H 3.902412 1.924263 4.338611 N 1.386854 3.137265 0.793667 O 1.197642 4.327345 0.962205 C 1.721420 0.825448 1.810916 H 1.464259 0.497952 2.828751 C 2.123444 2.265231 1.810440 H 2.130365 2.698618 0.807626 H 3.153412 2.288779 2.201457 O 1.240640 3.027803 2.661469 C 1.567858 4.269307 3.126482 O 0.744422 4.881793 3.760316 C 2.959406 4.798037 2.830093 H 3.178875 4.794095 1.756973 H 3.724763 4.189578 3.325948 H 3.019089 5.818384 3.209379 C 1.472405 1.816856 2.131463 C 1.718675 1.239036 0.716688 C 1.422840 0.624827 1.990485 C 1.192710 0.546659 2.985073 H 2.386896 2.314675 2.467784 H 1.900832 0.458047 3.813683 C 2.558979 0.036704 1.097701 H 2.788023 0.675 031 0.237466 C 0.536400 0.473110 0.104911 C 0.377528 0.695406 0.873700 H 2.184216 1.943696 0.023962 H 1.626988 1.586817 2.463314 H 0.424252 0.472371 0.970197 H 0.131167 1.651686 0.436994 H 0.187012 0.541473 3.408800 H 0.661402 2.538504 2.168086 O 3.741159 0.184493 1.855191 C 4.920496 0.419422 1.214555 C 5.048312 0.658520 0.161019 C 6.065099 0.412474 2.028398 C 6.313387 0.878240 0.707955 H 4.177652 0.689688 0.805120 C 7.317106 0.634274 1.474182 H 5.944567 0.222190 3.089863 C 7.451050 0.864978 0.098177 H 6.410626 1.061793 1.772894 H 8.198583 0.616962 2.107256 C 8.803 997 1.153393 0.482767 F 9.161170 2.450891 0.323439 F 9.771969 0.414223 0.108015 F 8.852050 0.897117 1.810538 TS17E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2563.0237512100 a.u. M06/SDD/6 311++G(d,p) SCF energy in s olution: 2562.1635502400 a.u Ru 1.993862 0.186244 0.852770 O 3.511683 1.376643 1.646983 O 2.956278 0.352892 2.835833 N 2.587876 0.409722 1.985553 N 0.782516 0.837956 1.960181 C 1.669882 0.161686 1 .151829 C 2.344224 0.187437 3.412120 C 3.912678 0.770903 1.471132 C 4.875255 0.440976 1.607487 C 6.249588 0.101105 0.997791 C 6.843586 1.127638 1.713055 C 5.886440 2.325858 1.548849 C 4.529471 1.981930 2.208697 C 5.695252 2.617475 0.043436 C 5.075685 1.379803 0.665428 C 3.703257 1.137169 0.002403 C 6.055896 0.198180 0.500418 C 0.094470 1.934557 1.649413 C 0.454585 3.175901 1.2540 77 C 0.405518 4.269686 1.122638 C 1.931996 3.355452 0.995773 C 1.167584 0.790936 3.392721 C 1.461252 1.823664 1.965179 C 1.779264 4.175096 1.377320 C 2.283183 2.945682 1.802624 C 2.064364 0 .548209 2.509584 C 2.686791 5.367264 1.184961 H 3.198845 2.114894 0.001897 H 2.095198 1.132156 3.910289 H 3.226601 0.229387 3.907055 H 4.439534 1.302652 1.089237

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203 H 4.992925 0.711317 2.666853 H 6.919834 0.961880 1.121820 H 7.002270 0.911327 2.779393 H 7.826220 1.371311 1.287403 H 6.309333 3.209148 2.045377 H 3.841809 2.836657 2.149367 H 4.685865 1.761360 3.275274 H 5.049658 3.495937 0.094334 H 6.666244 2.862189 0.409449 H 4.939698 1.607971 1.727904 H 5.686271 0.694228 1.011194 H 7.020243 0.458462 0.958318 H 0.013362 5.227029 0.819195 H 2.541841 2.955033 1.814375 H 2.253357 2.844585 0.082233 H 2.174295 4.417229 0.890321 H 1.446432 1.797062 3.728768 H 0.325289 0.455310 4.004340 H 3.344178 2.850403 2.022987 H 2.252597 0.633506 3.588323 H 3.025479 0.33 1977 2.032742 H 1.405058 0.310115 2.357756 H 3.007249 5.452893 0.138194 H 3.590731 5.286533 1.797443 H 2.180838 6.303197 1.445970 N 3.678072 0.716096 2.735524 O 4.456379 1.056805 3.604956 C 0.772032 1.621811 1.073935 H 0.987037 2.328506 1.887933 C 0.212817 2.198264 0.106397 H 0.655872 1.442252 0.545652 H 0.371730 2.887368 0.521649 O 1.269451 2.918936 0.783095 C 2.046277 3.838095 0.138461 O 3.046227 4.231845 0.689706 C 1.599656 4.325939 1.226400 H 1.535108 3.503840 1.947786 H 0.613814 4.802051 1.175548 H 2.331031 5.054264 1.577260 C 1.293408 2.240134 3.157275 C 0.71 4445 1.941379 1.732385 C 1.384565 0.105264 2.460779 C 1.728326 0.831960 3.663689 H 2.152478 2.911819 3.077901 H 2.803535 0.794764 3.861666 C 1.676453 0.829741 1.268237 H 1.412160 0.398823 0. 301567 C 0.571488 1.172994 2.015559 C 0.143010 0.135879 2.440673 H 0.642342 2.813459 1.087118 H 1.875523 1.075963 2.487874 H 1.333335 1.702916 2.578414 H 0.649351 0.624943 3.266658 H 1.211093 0.520574 4.576371 H 0.547981 2.716439 3.801211 O 2.997447 1.370250 1.206969 C 4.052778 0.624245 0.777479 C 4.028568 0.760001 0.565428 C 5.242718 1.339982 0.557920 C 5.184318 1.415956 0.13622 9 H 3.136530 1.339329 0.759477 C 6.384735 0.679971 0.128138 H 5.244418 2.410383 0.737077 C 6.362954 0.704931 0.088532 H 5.156901 2.492283 0.002250 H 7.302236 1.237223 0.032957 C 7.590042 1.393281 0.608586 F 7.703308 1.274554 1.956661 F 8.722165 0.865907 0.085153 F 7.592124 2.715420 0.334070 TS18E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2562.9950422800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solutio n: 2562.1327293500 a.u Ru 1.621134 0.844753 0.173272 O 2.053652 1.555799 2.334434 O 1.024408 2.842402 0.921318 N 4.028492 0.596936 0.584355 N 2.604747 2.228101 0.267630 C 2.737496 0.854902 0.22935 7 C 4.827082 1.773372 0.928789 C 4.647253 0.692637 0.280058 C 5.325995 0.631623 1.115786 C 5.921520 2.005647 1.479040 C 6.950927 2.423889 0.411302 C 6.255064 2.501379 0.962833 C 5.708155 1. 102469 1.329861 C 5.101661 3.526377 0.894108 C 4.057083 3.084782 0.170956 C 3.512093 1.714436 0.297541 C 4.774980 3.031810 1.538326 C 1.653597 3.085471 0.378652 C 1.579558 3.117212 1.790361 C 0.766237 4.082825 2.388932 C 2.357043 2.155110 2.656729 C 3.890420 2.917014 0.545018 C 0.969208 4.040463 0.397519 C 0.049479 5.025521 1.642040 C 0.170897 4.989453 0.252335 C 1.082450 4.08637 5 1.904598 C 0.840057 6.038654 2.323532 H 3.243339 1.850077 1.354740 H 5.072121 1.770770 1.998046 H 5.767086 1.794061 0.369055 H 4.579975 0.338317 1.862983 H 6.116884 0.132732 1.113927 H 6. 410847 1.937402 2.459499 H 7.781235 1.703875 0.374983

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204 H 7.384457 3.399490 0.668530 H 6.979027 2.811255 1.728002 H 5.250973 1.115561 2.328745 H 6.538310 0.381151 1.358841 H 4.622216 3.625221 1.877791 H 5.503537 4.515959 0.635343 H 3.246901 3.820256 0.202104 H 4.084839 2.764942 2.341325 H 5.175324 4.027271 1.775167 H 0.702368 4.107673 3.474827 H 3.411778 2.099329 2.362460 H 1.957414 1.137577 2.592827 H 2.319237 2.468822 3.704285 H 4.219993 3.448689 0.356458 H 3.767843 3.653733 1.343424 H 0.367705 5.719298 0.348880 H 1.788973 4.862343 2.229677 H 0.115662 4.327139 2.359743 H 1.430922 3.134369 2.312801 H 1.813167 5.599773 2.580591 H 1.030789 6.903028 1.679366 H 0.393431 6.400979 3.256066 N 1.527588 2.704295 2.105205 O 1.505713 3.599455 2.927745 C 0.716 021 0.963830 1.496291 H 0.471961 1.983485 1.824956 C 0.618793 0.021496 2.654857 H 0.647563 1.025803 2.349328 H 1.507508 0.221253 3.275415 O 0.578140 0.299088 3.412738 C 0.820860 0.276021 4.6 25503 O 1.863370 0.033002 5.181840 C 0.246974 1.183532 5.207863 H 0.488007 2.009444 4.529953 H 1.174518 0.631158 5.398033 H 0.127448 1.585234 6.149620 C 1.876619 1.339681 0.769834 C 2.098319 0.173909 0.556435 C 1.587809 0.604893 1.525498 C 1.545913 1.870872 0.652177 H 2.797754 1.782933 1.159223 H 2.303307 2.581407 0.994777 C 2.778528 0.160367 0.861110 H 2.929297 1.160888 1.280893 C 0.842732 0.942179 0.115124 C 0.510618 0.431157 1.189962 H 2.639382 0.661620 1.368415 H 1.693570 0.796696 2.595648 H 0.888122 2.021479 0.223899 H 0.276750 1.118766 1.992252 H 0.578091 2.3 50535 0.705643 H 1.088821 1.545850 1.492128 O 3.982877 0.587092 0.961331 C 5.184661 0.015422 0.726821 C 5.342402 1.288808 0.165260 C 6.316853 0.733052 1.086647 C 6.625212 1.804823 0.023091 H 4.483569 1.876783 0.135611 C 7.587527 0.212099 0.891871 H 6.171542 1.715131 1.524782 C 7.750595 1.064943 0.338140 H 6.744813 2.792996 0.454416 H 8.459078 0.790549 1.181610 C 9.131404 1.596028 0.086968 F 9.660329 1.112075 1.063424 F 9.989049 1.250477 1.076174 F 9.148868 2.944221 0.012311 TS19E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2562.9954496800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2562.1330363600 a.u Ru 1.679565 0.767330 0.390083 O 1.459027 2.559073 1.051219 O 1.183620 2.816706 1.086328 N 3.940402 0.726739 0.654871 N 2.243114 1.960310 1.281141 C 2.578259 0.801669 0.611692 C 4.601138 1.860020 1.303010 C 4.619346 0.552626 0.447433 C 4.777230 1.283335 1.808890 C 5.421549 2.667052 1.600927 C 6.798566 2.501184 0.929930 C 6.621444 1.795499 0.429931 C 6.018039 0.390 417 0.194479 C 5.684278 2.640478 1.321732 C 4.289956 2.782583 0.647050 C 3.728838 1.347957 0.506449 C 4.491646 3.505060 0.704053 C 1.004270 2.354641 1.887313 C 0.452562 1.581890 2.934258 C 0.663703 2.083514 3.609682 C 1.037257 0.251968 3.346134 C 3.419206 2.611916 1.910461 C 0.475317 3.622637 1.575372 C 1.228790 3.326638 3.302788 C 0.638545 4.081631 2.287712 C 1.078797 4.507667 0.508239 C 2.451831 3.824622 4.036508 H 3.853143 0.886167 1.496210 H 5.144196 2.460681 0.562545 H 5.319930 1.527140 2.057448 H 3.789824 1.396013 2.271041 H 5.397177 0.679014 2.487205 H 5.540 848 3.158273 2.575557 H 7.471870 1.918373 1.575083 H 7.266859 3.483826 0.784874 H 7.597598 1.684817 0.920238 H 5.926855 0.155655 1.143318

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205 H 6.688327 0.191837 0.455232 H 5.580565 2.175775 2.3 11866 H 6.125787 3.634057 1.481363 H 3.640114 3.377864 1.296369 H 3.539245 3.668934 1.213177 H 4.935456 4.493691 0.523263 H 1.095409 1.489543 4.412570 H 2.123332 0.307790 3.485898 H 0.855285 0.522024 2.593234 H 0.596409 0.082494 4.290020 H 3.358742 2.495901 3.000302 H 3.433136 3.681471 1.686493 H 1.053767 5.056053 2.037824 H 1.727425 5.279016 0.945656 H 0.295486 5.031505 0.050062 H 1.683208 3.933049 0.198176 H 3.372024 3.448678 3.569867 H 2.506659 4.918194 4.030283 H 2.457804 3.489016 5.079128 N 1.226624 3.369416 0.081852 O 1.064413 4.563801 0.241976 C 1.436184 0.1 17261 2.058182 H 1.483616 0.527413 2.946687 C 1.595584 1.549163 2.464691 H 1.346026 2.245549 1.662251 H 2.664178 1.672431 2.704947 O 0.798289 1.818322 3.637595 C 0.906054 2.983120 4.338488 O 0.173846 3.160717 5.280771 C 1.955010 3.986198 3.894230 H 1.820156 4.275955 2.846551 H 2.965067 3.572270 3.994897 H 1.868023 4.868772 4.528262 C 1.577792 1.784256 1.262244 C 1.621127 0.419511 1.985227 C 1.989933 0.110781 0.202208 C 1.852633 1.421367 0.223064 H 2.363078 2.426779 1.669837 H 2.784601 1.873433 0.575015 C 2.739537 0.302524 1.170209 H 2.863835 1.351956 1.459184 C 0.488157 0.541344 1.586379 C 0.716107 0.855664 0.200488 H 1.774571 0.487308 3.062783 H 2.477985 0.527994 1.085876 H 0.315845 1.374209 2.261105 H 0.665139 1.884539 0.131539 H 1.054834 1.730155 0.884738 H 0.629998 2.301117 1.402026 O 3.977518 0.382252 1.301657 C 5.127782 0.188485 0.842406 C 5.196606 1.399848 0.142166 C 6.305052 0.530540 1.107535 C 6.436671 1.884120 0.277439 H 4.301 303 1.964152 0.089533 C 7.531088 0.042798 0.681107 H 6.228749 1.467822 1.649054 C 7.605809 1.171515 0.015483 H 6.486561 2.820106 0.823500 H 8.436333 0.606931 0.883012 C 8.944888 1.707802 0.4 28345 F 9.604279 2.280976 0.607794 F 9.752957 0.727989 0.899042 F 8.842930 2.647203 1.395137 TS20* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8308654600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8666786000 a.u Ru 2.286589 0.065806 0.569950 O 3.608364 1.376134 2.086397 O 1.771560 0.386649 2.682001 N 3.870656 1.482473 1.300442 N 2.878975 0.013792 2.555991 C 3.055655 0.400241 1.259143 C 4.160128 1.961330 2.653293 C 4.168041 2.222945 0.071692 C 3.277313 3.480383 0.071242 C 3.545235 4.153705 1.434091 C 5.025601 4.582503 1.500663 C 5.925364 3.338191 1.347537 C 5.649698 2.67 3272 0.020316 C 5.620160 2.345900 2.490016 C 4.133200 1.907910 2.421280 C 3.910590 1.215149 1.062998 C 3.247128 3.157097 2.575071 C 2.423377 1.297975 3.009851 C 1.213782 1.383865 3.723336 C 0.806733 2.634952 4.202168 C 0.367909 0.162262 4.002496 C 3.698027 0.773821 3.506916 C 3.242973 2.434406 2.836515 C 1.573850 3.786611 4.010635 C 2.794811 3.659552 3.337816 C 4.568730 2.355127 2.112766 C 1.095615 5.134623 4.495007 H 4.692929 0.445982 0.967956 H 5.221932 2.188273 2.782839 H 3.587776 2.873450 2.870978 H 2.226359 3.185293 0.016778 H 3.489289 4.189019 0.742599 H 2.901171 5.038295 1.531737 H 5.245862 5.312000 0.708164 H 5.231466 5.079275 2.458199 H 6.980446 3.639093 1.389286 H 6.301337 1.800895 0.161977 H 5.874274 3.386861 0.827273 H 6.273661 1.466593 2.416273 H 5.830688 2.821342 3.458352

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206 H 3.930640 1.213943 3.243257 H 2.192947 2.863088 2.574860 H 3.442008 3.638503 3.543541 H 0.135958 2.708499 4.740132 H 0.760447 0.411202 4.853165 H 0.339 108 0.519330 3.146635 H 0.657859 0.448640 4.254672 H 3.104350 1.073061 4.374997 H 4.540407 0.167916 3.864603 H 3.416189 4.541017 3.195035 H 5.219689 1.577105 2.528212 H 5.101752 3.307467 2.1 85636 H 4.439762 2.123227 1.048799 H 0.637703 5.703183 3.675406 H 1.923555 5.737211 4.884365 H 0.345547 5.034580 5.286017 N 2.799087 1.088916 3.034639 O 2.964693 1.452705 4.185964 C 3.986240 2.570954 2.048643 H 4.108608 2.508905 3.128676 C 5.253136 2.898018 1.313471 H 5.915734 2.021495 1.298485 H 5.064524 3.190278 0.275098 O 5.881417 3.976427 2.029317 C 7.126084 4.426922 1.697547 O 7.597410 5.333602 2.338765 C 1.222191 3.428753 0.159665 C 2.358933 2.399575 0.074732 C 0.378498 1.327419 1.081967 C 0.421512 2.862242 1.335134 H 1.617104 4.432275 0.347436 H 0.957550 3.0 34354 2.276712 C 1.799743 1.042597 0.491903 H 1.772150 0.271328 0.283883 C 2.778421 2.341811 1.519199 C 0.734686 0.929144 0.129636 H 3.208983 2.663531 0.562138 H 0.267750 0.783332 2.022632 H 1.970785 2.101683 2.213957 H 0.530443 1.272158 0.898207 H 0.567007 3.310429 1.436102 H 0.589998 3.499333 0.735482 O 2.585994 0.564294 1.593217 C 3.739492 0.133851 1.391304 C 4.308042 0.410536 0.140705 C 4.366952 0.600320 2.559105 C 5.491203 1.148703 0.070092 H 3.853040 0.049985 0.773536 C 5.544828 1.328164 2.476341 H 3.905286 0.384281 3.517127 C 6.116620 1.609003 1.228006 H 5.9 23217 1.371905 0.900141 H 6.019362 1.691704 3.382081 C 7.423597 2.341937 1.145905 F 8.481996 1.500343 1.260857 F 7.551246 3.257634 2.131855 F 7.569762 2.987406 0.033145 C 7.843072 3.756037 0 .541175 H 7.252406 3.796040 0.380663 H 8.043623 2.700098 0.755777 H 8.790249 4.272725 0.385556 C 0.383437 1.357030 0.195259 C 1.477928 2.165181 0.110499 H 0.156200 1.114547 1.226224 H 0.445828 1.326660 0.505329 H 2.094585 2.512466 0.709801 C 1.408871 3.124850 1.274261 H 0.824016 2.706036 2.098972 H 2.408992 3.377390 1.629251 O 0.752313 4.310262 0.764521 C 0.679940 5.452986 1.504744 O 0.133440 6.416224 1.022649 C 1.296131 5.444565 2.891006 H 0.902087 4.630663 3.508871 H 2.383095 5.313161 2.839243 H 1.075902 6.401409 3.364863 TS21* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8156203500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8589377600 a.u Ru 2.478526 0.456632 0.250783 O 3.222815 3.583083 1.311612 O 1.551871 2.144660 1.205702 N 4.346739 1.748219 0.338894 N 3.26 5564 2.057021 1.540237 C 3.346588 1.257155 0.432836 C 4.851854 3.048858 0.108425 C 4.497846 1.194683 1.688575 C 3.502909 1.884883 2.660013 C 3.580534 1.236233 4.054386 C 5.016676 1.388459 4. 596737 C 6.006038 0.698916 3.634369 C 5.926304 1.370755 2.243455 C 5.638034 0.794569 3.518974 C 4.198973 0.950043 2.960541 C 4.163895 0.312690 1.553129 C 3.218130 0.257541 3.928628 C 2.269737 2.057345 2.574388 C 1.113364 2.850963 2.388841 C 0.142412 2.869101 3.391714 C 0.939860 3.722584 1.164312 C 4.310787 3.105727 1.545137 C 2.484234 1.381072 3.789678 C 0.295827 2.148225 4.583639 C 1.477206 1.429216 4.765467 C 3.762844 0.640988 4.114130 C 0.785488 2.156244 5.638452 H 4.977456 0.766623 0.972994

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207 H 5.943195 3.089932 0.069370 H 4.455458 3.861091 0.517758 H 2.48492 0 1.791804 2.252976 H 3.723897 2.960378 2.725918 H 2.875484 1.739771 4.729361 H 5.269380 2.452856 4.706609 H 5.090839 0.938072 5.595329 H 7.028603 0.803367 4.019978 H 6.648859 0.913484 1.554 159 H 6.186494 2.436232 2.335223 H 6.350400 1.313400 2.863590 H 5.710152 1.270368 4.507183 H 3.971033 2.014674 2.888169 H 2.185568 0.371220 3.572595 H 3.262750 0.738463 4.915217 H 0.748369 3.477824 3.249008 H 1.572630 4.618586 1.223822 H 1.209371 3.207073 0.237748 H 0.094473 4.068091 1.075819 H 3.884541 4.077585 1.807448 H 5.082901 2.861748 2.286527 H 1.635765 0.894044 5.699473 H 4.192300 1.024533 5.047470 H 3.578535 0.429463 4.261781 H 4.515592 0.748748 3.330034 H 1.568637 1.422517 5.406329 H 0.384677 1.903357 6.624996 H 1.270347 3.136157 5.708295 N 2.102049 3.229 430 1.716914 O 1.449517 3.842853 2.557743 C 4.182816 2.751851 0.629445 H 4.267136 3.336957 1.543779 C 5.424239 2.762961 0.213909 H 6.214817 2.169839 0.266556 H 5.249689 2.343346 1.209626 O 5.842294 4.137063 0.317778 C 7.003801 4.485098 0.943655 O 7.298877 5.653760 0.997179 C 1.503021 1.859978 1.648316 C 2.684045 1.264461 0.821025 C 0.725303 0.303360 0.858094 C 0.650770 0.651226 2.068170 H 1.862672 2.451286 2.496231 H 1.095781 0.152790 2.936492 C 2.216399 0.184601 0.433166 H 2.354660 0.404516 0.631043 C 3.034653 2.113128 0.371973 C 0.187385 0.093120 0.293144 H 3.554185 1.147823 1.472624 H 0.517288 1.336582 1.137046 H 2.235412 2.212700 1.109078 H 0.271009 1.155276 0.504797 H 0.373515 0.925336 2.342764 H 0.917426 2.541087 1.018449 O 2.915490 1.170279 1.208585 C 4.178321 1.546191 0.867784 C 4.917644 1.012839 0.197710 C 4.740487 2.556376 1.667440 C 6.203292 1.493922 0.453264 H 4.510449 0.228290 0.824066 C 6.019802 3.022914 1.405778 H 4.14 7011 2.963518 2.479521 C 6.762457 2.494215 0.340585 H 6.769512 1.088121 1.285484 H 6.443614 3.809855 2.021405 C 8.168428 2.960452 0.102751 F 9.059859 2.300096 0.884163 F 8.316808 4.275813 0. 378973 F 8.559356 2.766444 1.177636 C 7.855645 3.376978 1.533491 H 7.297195 2.782935 2.265389 H 8.209292 2.689887 0.756402 H 8.715794 3.834995 2.022029 C 0.542993 0.772870 1.300452 C 3.131125 1.347733 1.221632 H 0.870046 0.405795 2.266124 H 0.299198 1.829105 1.230111 H 3.652379 0.827549 2.030599 C 3.081791 2.822048 1.499273 H 2.253558 3.327443 1.002443 H 4.013839 3.268151 1.12596 7 O 2.985384 2.958153 2.935877 C 3.078140 4.172872 3.552926 O 2.982982 4.210495 4.755827 C 3.300981 5.392675 2.682161 H 2.517272 5.498289 1.924403 H 4.256407 5.329109 2.149097 H 3.307303 6. 272866 3.325359 14* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8472462500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8917672300 a.u Ru 2.423973 0.478316 0.347780 O 3.438219 3.152338 1.230420 O 1.624140 1 .984351 1.658712 N 4.458702 1.535789 0.151434 N 3.177037 1.677156 1.916724 C 3.336296 1.024734 0.727854 C 4.993930 2.710718 0.846178 C 4.705219 1.238808 1.259679 C 3.980257 2.271064 2.165186 C 4.144037 1.885293 3.647023 C 5.645993 1.857202 3.997793 C 6.366223 0.827994 3.101566 C 6.209003 1.234813 1.617698 C 5.746691 0.565378 3.332353 C 4.236558 0.541818 2.972013 C 4.125048 0.166398 1.484381

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208 C 3.524985 0.491469 3.868403 C 2.167091 1.502819 2.922451 C 1.038176 2.348882 2.899031 C 0.060404 2.183769 3.885521 C 0.903651 3.469077 1.891277 C 4.297457 2.599044 2.206367 C 2.362313 0.590580 3.978536 C 0.188713 1.232510 4.904011 C 1.354327 0.462311 4.941017 C 3.634111 0.215108 4.137539 C 0.899077 1.040053 5.934382 H 4.704480 0.893543 0.883648 H 6.083493 2.67 0546 0.923230 H 4.719910 3.634447 0.317510 H 2.917009 2.298818 1.892018 H 4.390313 3.275668 1.989307 H 3.631477 2.627530 4.272983 H 6.085969 2.855307 3.862067 H 5.780302 1.590584 5.054476 H 7.434848 0.805207 3.350961 H 6.740358 0.529063 0.965618 H 6.649751 2.229432 1.455667 H 6.262514 1.321676 2.726598 H 5.871357 0.858524 4.383889 H 3.820663 1.534348 3.148160 H 2.450793 0.509421 3.643378 H 3.623520 0.198582 4.922167 H 0.816826 2.827215 3.867008 H 1.487117 4.345704 2.205457 H 1.261961 3.186994 0.897911 H 0.137074 3.794679 1.802157 H 3.924105 3.554871 2.583286 H 4.95 2297 2.160334 2.970531 H 1.488091 0.261694 5.741911 H 4.287121 0.246501 4.890365 H 3.411417 1.229887 4.482926 H 4.203312 0.292045 3.207863 H 1.532863 0.180398 5.680683 H 0.479580 0.847395 6. 927633 H 1.547882 1.919156 6.002807 N 2.366598 3.052137 1.864990 O 1.960948 3.889144 2.663042 C 3.913373 2.805740 0.819925 H 3.989850 3.217183 1.825137 C 5.150647 2.996849 0.007787 H 5.959422 2.352483 0.363946 H 4.984181 2.751982 1.061462 O 5.528713 4.379780 0.130916 C 6.673930 4.869479 0.424786 O 6.937089 6.035979 0.263011 C 1.282217 2.327477 1.605169 C 2.434881 1.575032 0.874195 C 0.468375 0.057175 1.254559 C 0.437806 1.225604 2.265114 H 1.671189 3.061178 2.318572 H 0.908147 0.899519 3.200321 C 1.937997 0.089843 0.749649 H 2.038768 0.297482 0.270776 C 2.7776 14 2.199807 0.451891 C 0.551420 0.232401 0.126654 H 3.315267 1.554362 1.522426 H 0.297932 0.904218 1.741982 H 1.981224 2.147143 1.196607 H 0.476938 1.212776 0.344765 H 0.578643 1.554404 2.50 5314 H 0.682715 2.888216 0.877231 O 2.665551 0.772045 1.642490 C 3.919893 1.196279 1.332885 C 4.640028 0.822032 0.189959 C 4.497430 2.084617 2.257837 C 5.922624 1.335434 0.016082 H 4.221682 0.133391 0.534295 C 5.771846 2.585443 2.043281 H 3.918922 2.370633 3.130234 C 6.496543 2.213267 0.901548 H 6.474405 1.050500 0.905862 H 6.206852 3.277376 2.757808 C 7.895918 2.719516 0.714111 F 8.784189 2.049479 1.491034 F 8.007294 4.025730 1.048597 F 8.320579 2.589093 0.563045 C 7.548633 3.915371 1.216097 H 6.999577 3.460199 2.047874 H 7.923713 3.100340 0.586710 H 8.394315 4.47 9741 1.609311 C 0.555900 0.910404 0.978999 C 1.963573 1.543817 1.291225 H 0.207209 0.453174 1.908112 H 0.115569 1.709558 0.656451 H 2.373550 1.164999 2.221095 C 2.006989 3.057203 1.312378 H 1.414446 3.495451 0.507055 H 3.037397 3.412735 1.227565 O 1.457536 3.443446 2.597346 C 1.310697 4.753232 2.945964 O 0.896962 5.010778 4.051479 C 1.666352 5.805957 1.914343 H 1.026511 5.722717 1.028463 H 2.702172 5.706441 1.572662 H 1.525188 6.787369 2.367555 TS22* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8398525900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8714191900 a.u Ru 1.992754 0.490593 0.562683 O 2.785352 0.708339 2.958152 O 1.212664 1.894491 2.036022 N 4.074387 0.112284 1.435301

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209 N 2.836480 1.671756 1.699863 C 3.002014 0.549272 0.923892 C 4.580214 0.448030 2.690992 C 4.399807 1.467412 0.981336 C 3.797296 2.536364 1.927351 C 4.069053 3.945950 1.362302 C 5.592642 4.165490 1.263072 C 6.204133 3.100331 0.328861 C 5.930736 1.693245 0.907536 C 5.568067 3.225682 1.070412 C 4.036773 2.998981 0.973141 C 3.798590 1.577352 0.427034 C 3.437579 4.065798 0.039304 C 2.073523 2.863777 1.445853 C 0.876102 3.082567 2.156806 C 0.189584 4.286334 1.959330 C 0.307 523 2.070103 3.126179 C 3.921977 1.826687 2.695808 C 2.607530 3.870693 0.611849 C 0.663092 5.276836 1.095459 C 1.877177 5.051331 0.439730 C 3.940004 3.732222 0.093049 C 0.116290 6.550735 0.8 66962 H 4.367108 0.879921 1.066692 H 5.672206 0.496848 2.699488 H 4.258534 0.166294 3.543085 H 2.720510 2.360682 2.022702 H 4.238442 2.447345 2.930718 H 3.631704 4.694705 2.036796 H 6.051743 4.106656 2.260410 H 5.803689 5.170536 0.873617 H 7.289561 3.250487 0.259387 H 6.383472 0.920529 0.272296 H 6.390201 1.611187 1.903971 H 6.011816 2.494526 1.758956 H 5.776619 4.222254 1.484486 H 3.604497 3.106038 1.971265 H 2.351636 3.935230 0.011877 H 3.622286 5.069759 0.445789 H 0.737944 4.453870 2.503444 H 0.102609 2.572651 4.008875 H 1.058386 1.348430 3.456176 H 0.514933 1.5 02356 2.671506 H 3.511174 2.112554 3.668392 H 4.613011 2.615111 2.372341 H 2.269983 5.808472 0.234634 H 4.726124 4.271150 0.453075 H 3.879086 4.162478 1.097059 H 4.255502 2.690779 0.191594 H 0.728090 6.480381 0.041982 H 0.550097 7.410851 0.741390 H 0.793809 6.762346 1.700581 N 1.943924 1.649938 3.083668 O 1.808917 2.304161 4.105374 C 5.058121 3.208332 1.401892 H 5.919606 3.173853 2.066387 C 5.412829 3.423489 0.039206 H 5.864988 2.510183 0.450513 H 4.537256 3.667674 0.649811 O 6.368642 4.499501 0.078405 C 6.983013 4.868431 1.238538 O 7.781509 5.772373 1.204564 C 1.4 06102 3.832072 1.925851 C 2.517927 3.043062 1.195917 C 0.415686 1.983908 0.562596 C 0.067410 3.131339 1.559933 H 1.417257 4.885354 1.630817 H 0.656584 3.814902 1.115627 C 1.871549 1.651026 0 .980858 H 1.857706 1.075912 1.915282 C 3.835410 3.033107 1.917035 C 0.607421 0.871561 0.673707 H 2.644378 3.455564 0.187903 H 0.436683 2.381457 0.457229 H 3.767438 2.857865 2.992479 H 0.518114 0.348658 1.636394 H 0.400245 2.715681 2.460978 H 1.571069 3.808684 3.009526 O 2.549730 0.916107 0.041995 C 3.450464 0.072923 0.238260 C 3.906281 0.426310 1.515485 C 3.916149 0.779462 0.883731 C 4.808337 1.481148 1.658217 H 3.591967 0.119194 2.395927 C 4.815503 1.825163 0.729739 H 3.551260 0.494232 1.865303 C 5.264700 2.188320 0.546052 H 5.156710 1.752931 2.649247 H 5.16055 9 2.372329 1.601086 C 6.273853 3.288252 0.702612 F 7.542862 2.840135 0.546950 F 6.095073 4.266580 0.214756 F 6.211066 3.862088 1.926014 C 6.623394 4.116146 2.506340 H 5.549581 4.170141 2.717 309 H 6.890067 3.055832 2.429260 H 7.175743 4.563473 3.332865 C 0.025780 0.869708 0.598493 C 0.809487 0.921280 1.770524 H 0.921624 0.348908 0.645177 H 0.105005 1.664575 0.133962 H 0.443655 0.338340 2.613077 C 1.594521 2.134556 2.180892 H 2.475398 1.863367 2.767071 H 1.890770 2.737803 1.329165 O 0.719572 2.934534 3.033108 C 1.198489 4.139151 3.401217 O 2.266851 4.588316 3.036178

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210 C 0.234990 4.843471 4.330093 H 0.765442 4.880786 3.887785 H 0.155736 4.287772 5.270792 H 0.595795 5.852808 4.531795 TS23* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8457632300 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 2907.8847012100 a.u Ru 2.004646 0.177773 0.605042 O 1.731344 3.756659 2.297907 O 1.238228 1.647050 2.033570 N 4.070618 0.746247 1.186459 N 2.347493 1.942393 1.808441 C 2.770737 1.019305 0.886328 C 4.537039 1.349038 2.438331 C 4.749365 0.382878 0.550803 C 4.658144 1.656091 1.437053 C 5.306514 2.853941 0.714777 C 6.786337 2.531617 0.423116 C 6.874814 1.272193 0.4635 91 C 6.241345 0.075573 0.279071 C 6.116499 1.520835 1.781713 C 4.625802 1.844724 1.489031 C 4.012490 0.629937 0.774930 C 4.553226 3.106349 0.604257 C 1.157296 2.748884 1.833991 C 0.080066 2 .376964 2.662722 C 1.049693 3.203531 2.700652 C 0.127451 1.168257 3.572131 C 3.433534 2.370873 2.718206 C 1.146537 3.990030 1.158582 C 1.126382 4.392837 1.971635 C 0.008896 4.774736 1.222070 C 2.346951 4.524116 0.405112 C 2.375850 5.241436 1.986018 H 4.131888 0.267499 1.425776 H 5.521701 1.808901 2.319414 H 4.606987 0.590258 3.228882 H 3.601923 1.867997 1.651864 H 5.160910 1.4794 93 2.398258 H 5.241055 3.739442 1.360601 H 7.335933 2.374548 1.362301 H 7.260356 3.380753 0.086282 H 7.926984 1.041808 0.675569 H 6.322520 0.840449 0.321406 H 6.778031 0.101511 1.222461 H 6 .189936 0.641597 2.436294 H 6.571987 2.360134 2.324350 H 4.122000 2.018941 2.440539 H 3.508702 3.371931 0.409421 H 4.998063 3.956590 1.137397 H 1.886351 2.913887 3.334117 H 0.147303 1.484582 4.623184 H 1.008229 0.549052 3.391848 H 0.762376 0.540033 3.448789 H 3.085962 2.360890 3.755364 H 3.744634 3.393260 2.473196 H 0.033061 5.706819 0.663014 H 2.903554 5.236731 1.028942 H 2.024417 5.053186 0.495850 H 3.039636 3.733633 0.104612 H 2.957935 5.083556 2.900302 H 3.024869 4.999625 1.135473 H 2.134944 6.307530 1.916557 N 1.806740 2.602235 2.735095 O 2.347256 2.303319 3.805127 C 4.057518 4.776378 2.060426 H 4.832434 4.859069 2.821451 C 4.189432 5.789663 0.956677 H 3.567363 5.555716 0.088520 H 3.892065 6.781254 1.316304 O 5.567950 5.964536 0.579894 C 6.18 6236 5.140753 0.317197 O 7.374978 5.268732 0.481756 C 0.557044 3.891434 1.971977 C 1.924069 3.574078 1.321704 C 0.327226 1.999844 0.355545 C 0.478560 3.028586 1.202649 H 0.335470 4.962186 1. 936622 H 1.099252 3.629281 0.531746 C 1.763463 2.090610 0.935352 H 1.866294 1.466147 1.831124 C 3.102502 3.850315 2.210377 C 0.295927 0.610538 0.374953 H 2.004448 4.133684 0.382068 H 0.375432 2.357232 0.673896 H 3.151989 3.224122 3.104138 H 0.262093 0.189212 1.380657 H 1.154044 2.522479 1.902643 H 0.584261 3.609629 3.032753 O 2.766131 1.745075 0.033943 C 3.393705 0.536079 0.05256 3 C 3.569790 0.302566 1.057141 C 3.922936 0.154401 1.297004 C 4.223980 1.523755 0.903633 H 3.212897 0.015209 2.038948 C 4.575424 1.062103 1.440010 H 3.793931 0.824011 2.141128 C 4.718176 1. 918082 0.341098 H 4.357141 2.169913 1.765082 H 4.971448 1.351627 2.407833 C 5.326889 3.275064 0.515394 F 5.925258 3.719666 0.610508 F 6.237843 3.308233 1.508802 F 4.381681 4.214409 0.833867 C 5.337793 4.144796 1.083655 H 4.628097 4.664281 1.739152 H 4.760217 3.492371 0.422202

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211 H 6.007090 3.543378 1.699500 C 0.228809 0.442901 0.693930 C 0.836832 0.983190 1.730682 H 0.984824 0.07187 6 1.287160 H 0.647884 1.296080 0.158666 H 0.731527 0.482941 2.695557 C 0.913367 2.474160 1.893840 H 1.785368 2.765551 2.489303 H 0.937773 2.996755 0.944136 O 0.288335 2.883360 2.607945 C 0.504406 4.212936 2.700313 O 0.259214 5.053210 2.267823 C 1.823690 4.503480 3.376691 H 2.640104 4.327329 2.666711 H 1.976601 3.841743 4.233478 H 1.847343 5.547626 3.692323 TS24* B3LYP/SDD/6 31G(d) SC F energy in gas p hase: 2908.8395835300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8682031800 a.u Ru 1.933181 0.481999 0.536090 O 2.192816 2.665416 0.095821 O 1.233602 2.160464 1.783004 N 4.299442 0.834168 0.497326 N 2.660025 1.605049 1.742170 C 2.958564 0.751782 0.701848 C 5.012438 1.654065 1.479626 C 4.967269 0.178093 0.332936 C 5.441730 1.364175 0.547633 C 6.078238 2.457975 0.333785 C 7.27 1649 1.869949 1.111884 C 6.777683 0.708340 1.997685 C 6.188155 0.396875 1.089279 C 5.707212 1.239151 2.978440 C 4.497318 1.807800 2.185374 C 3.917983 0.631345 1.362751 C 5.013827 2.977590 1.318021 C 1.513084 1.588016 2.607503 C 1.385397 0.533772 3.544159 C 0.317431 0.560607 4.442745 C 2.379355 0.604580 3.592161 C 3.859299 2.311991 2.251635 C 0.618761 2.673140 2.628312 C 0.6089 24 1.611815 4.463771 C 0.434384 2.654974 3.555379 C 0.735739 3.856688 1.693985 C 1.734310 1.628324 5.472338 H 3.836491 0.198237 2.076818 H 5.655903 2.387898 0.985414 H 5.644581 1.030631 2.12 5003 H 4.584359 1.775857 1.092150 H 6.172792 1.012929 1.290490 H 6.423459 3.279359 0.308088 H 8.046885 1.515490 0.417117 H 7.733005 2.648121 1.734879 H 7.620575 0.289546 2.563296 H 5.873943 1.263774 1.686149 H 6.964185 0.744398 0.390553 H 5.375961 0.434944 3.649808 H 6.148900 2.021679 3.611634 H 3.742853 2.173648 2.891755 H 4.201260 3.450892 0.763269 H 5.452655 3.746532 1.969173 H 0.215619 0.253177 5.158186 H 3.406905 0.242385 3.718578 H 2.364568 1.202224 2.673713 H 2.158430 1.270052 4.431936 H 3.942379 2.183117 3.335252 H 3.781596 3.386078 2.046389 H 1.129425 3.49 2304 3.567348 H 0.502770 4.787117 2.222634 H 0.023580 3.781564 0.862497 H 1.730471 3.957987 1.257208 H 2.243995 0.659034 5.521660 H 2.480032 2.391382 5.228595 H 1.359192 1.843987 6.481234 N 1.638754 3.087138 0.984965 O 1.500499 4.272926 1.232711 C 5.472095 3.714689 1.400676 H 6.379900 3.565376 1.983675 C 5.619229 4.743277 0.313315 H 4.788235 4.733222 0.396915 H 5.666925 5.747814 0.748879 O 6.884496 4.603893 0.360129 C 7.061754 3.744229 1.406512 O 8.180381 3.587673 1.831439 C 1.901687 3.634189 2.020019 C 3.012655 3.083285 1.099279 C 0.927563 1.971074 0.433737 C 0.573964 3.170071 1.368902 H 1.965932 4.720280 2.135097 H 0.121840 3.980274 0.793262 C 2.435188 1.705725 0.726338 H 2.538206 1.024630 1.577312 C 4.372740 3.025571 1.731328 C 0.077191 0.726799 0.640262 H 3.035983 3.680665 0.179261 H 0.881361 2.284969 0.613726 H 4.447881 2.347490 2.584413 H 0.243179 0.570317 1.665789 H 0.161984 2.879163 2.124000 H 2.016938 3.200763 3.022843 O 3.102 665 1.171102 0.424846 C 3.580519 0.104822 0.481874 C 3.896020 0.906561 0.624677 C 3.785937 0.605683 1.778396 C 4.362485 2.204755 0.425391 H 3.788743 0.535012 1.636534

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212 C 4.256689 1.898144 1.9 66449 H 3.555991 0.035489 2.623294 C 4.536342 2.713261 0.863339 H 4.603098 2.822546 1.284695 H 4.405973 2.277258 2.972047 C 4.943857 4.141549 1.060876 F 5.747854 4.586402 0.070786 F 5.587505 4.333691 2.231551 F 3.863038 4.975057 1.074698 C 5.839819 3.071911 2.001923 H 5.171420 3.814115 2.455224 H 5.262737 2.517591 1.256028 H 6.183046 2.389373 2.779911 C 0.253759 0.431662 0.131399 C 1.297646 0.888746 1.654753 H 0.939603 0.405644 0.972652 H 0.119012 1.401470 0.331119 H 0.769641 0.536821 2.555578 C 1.490611 2.364637 1.664924 H 2.398524 2.573302 2.254559 H 1.650292 2.7 81475 0.671744 O 0.362666 3.016736 2.295619 C 0.396422 4.373993 2.301699 O 1.304393 5.015768 1.818432 C 0.835498 4.946337 2.960860 H 1.712098 4.789711 2.322644 H 1.028398 4.445741 3.914385 H 0.694423 6.016405 3.118802 TS25* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8200144200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8586815800 a.u Ru 1.613489 0.851470 0.019801 O 0.946983 2.024425 2.109058 O 0.123379 2.439193 0.216537 N 4.047519 0.392654 1.454167 N 3.580782 1.612013 0.711420 C 3.182442 0.298525 0.662171 C 4.947676 0.457255 2.238005 C 3.764934 1.795499 1.778909 C 2.891762 1.899826 3.057075 C 2.520864 3.371330 3.326075 C 3.813823 4.192213 3.511940 C 4.673818 4.093907 2.234952 C 5.056425 2.614622 1.994732 C 3.868615 4.638262 1.034273 C 2.575366 3.804002 0.842472 C 2.995010 2.346330 0.559492 C 1.723945 3.912548 2.123713 C 3.145885 2.718285 0.093564 C 2.206256 3.629345 0.431619 C 1.786223 4.695208 0.371857 C 1.732942 3.557402 1.866072 C 4.806591 1.80 2004 1.517493 C 3.769373 2.970957 1.334417 C 2.306430 4.908062 1.652810 C 3.315087 4.050516 2.101861 C 4.959982 2.176207 1.826568 C 1.802756 6.037777 2.519990 H 3.709098 2.360183 0.277766 H 5.971641 0.074888 2.225461 H 4.616149 0.512074 3.284169 H 1.978604 1.299347 2.921240 H 3.427554 1.477495 3.919625 H 1.912428 3.428686 4.238440 H 4.379090 3.824686 4.380601 H 3.562647 5.241528 3.714852 H 5.592844 4.680520 2.363206 H 5.701106 2.520015 1.110690 H 5.624829 2.239548 2.859113 H 4.480709 4.603661 0.122303 H 3.615976 5.693456 1.208976 H 2.001613 4.194202 0.003249 H 0.78 7914 3.359169 1.994983 H 1.449389 4.961389 2.300008 H 1.049625 5.391129 0.025010 H 2.356676 4.202570 2.500499 H 1.793625 2.547449 2.277710 H 0.703909 3.915949 1.965508 H 4.687462 2.648180 2. 200450 H 5.660513 2.011373 0.861593 H 3.772448 4.224568 3.073285 H 5.888313 2.721803 1.609258 H 4.909553 2.025452 2.908095 H 5.034994 1.196202 1.349445 H 0.976994 5.703798 3.162103 H 2.590309 6.419269 3.178045 H 1.428296 6.871339 1.916668 N 0.695485 2.814470 1.167997 O 1.190078 3.933098 1.083364 C 2.818674 4.464461 1.548251 H 2.450910 5.342915 1.019125 C 3.955873 4.758994 2.48776 0 H 4.484641 3.855525 2.805365 H 3.584172 5.255097 3.391523 O 4.864772 5.722756 1.924957 C 5.843635 5.369613 1.039325 O 6.498481 6.248488 0.535178 C 1.497527 1.527850 3.060713 C 2.548081 1.960903 1.979812 C 1.250847 0.002074 1.164641 C 1.084585 0.084822 2.697828 H 1.912578 1.599731 4.070858 H 1.763986 0.633264 3.167327 C 2.586200 0.782346 0.963115 H 2.735417 1.113930 0.071253 C 2.222826 3.283338 1.334902 C 0.086560 0.666984 0.428128

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213 H 3.541272 2.005826 2.433343 H 1.364053 1.027209 0.823772 H 1.389107 3.268513 0.632128 H 0.434791 1.433471 0.994845 H 0.069109 0.157 936 3.031371 H 0.632048 2.197697 3.032021 O 3.708917 0.005788 1.382049 C 4.248256 0.971493 0.575878 C 3.736924 1.363493 0.663593 C 5.403842 1.588495 1.083193 C 4.372010 2.377552 1.383654 H 2.832704 0.933311 1.071967 C 6.036577 2.583825 0.353897 H 5.782200 1.271740 2.049931 C 5.522760 2.986321 0.886996 H 3.935513 2.703659 2.320758 H 6.926597 3.061942 0.751146 C 6.245933 4.036290 1.677689 F 7.337489 3.529377 2.307608 F 6.699701 5.038035 0.885792 F 5.468494 4.591152 2.630099 C 6.070104 3.895025 0.765901 H 6.395649 3.371326 1.672483 H 5.159277 3.405190 0.407677 H 6.852 009 3.810046 0.011056 C 0.032215 0.765078 0.955366 C 1.750228 0.709214 1.861303 H 0.643515 0.230821 1.615659 H 0.604779 1.581457 1.382922 H 1.061361 1.379479 2.389645 C 2.631537 0.065854 2.7 77637 H 3.657141 0.325386 2.728475 H 2.674273 1.127450 2.529180 O 2.131529 0.091644 4.126419 C 2.784729 0.586968 5.095064 O 3.743194 1.302735 4.886229 C 2.163453 0.328992 6.446697 H 1.106705 0.615022 6.436819 H 2.207347 0.739704 6.680939 H 2.698089 0.898576 7.207520 TS26* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8192242600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8566395600 a.u Ru 1.614333 0.872509 0.135810 O 0.635058 3.327493 2.254713 O 0.131456 2.100667 0.581542 N 3.997119 0.677816 1.463151 N 3.666823 1.413295 0.910509 C 3.205917 0.133583 0.711221 C 4.896248 0.039640 2.37013 1 C 3.633792 2.090886 1.617301 C 2.663802 2.285843 2.813115 C 2.220147 3.759524 2.903077 C 3.464965 4.651006 3.093692 C 4.421053 4.461179 1.898265 C 4.874042 2.984636 1.837993 C 3.690014 4. 842659 0.594348 C 2.444813 3.938146 0.398010 C 2.929827 2.476714 0.297059 C 1.495419 4.142089 1.597619 C 3.348324 2.615951 0.192432 C 2.464862 3.552854 0.767553 C 2.164739 4.718336 0.053692 C 1.925744 3.396916 2.171444 C 4.873245 1.446970 1.767568 C 4.034675 2.924659 1.002123 C 2.751352 5.001600 1.183653 C 3.700538 4.103543 1.679734 C 5.161307 2.070951 1.542847 C 2.377613 6.245236 1.955598 H 3.690207 2.427823 0.495134 H 5.895602 0.402322 2.378972 H 4.504761 0.022943 3.397028 H 1.783896 1.637934 2.675320 H 3.146536 1.973475 3.750679 H 1.543454 3.880660 3.759326 H 3.975616 4.398852 4.034316 H 3.161867 5.703689 3.167399 H 5.305973 5.097485 2.029754 H 5.585518 2.832725 1.015302 H 5.390325 2.722187 2.773849 H 4.367888 4.741748 0.264286 H 3.385514 5.897 790 0.636613 H 1.942318 4.215987 0.531200 H 0.589795 3.536799 1.471380 H 1.171399 5.190485 1.644799 H 1.470720 5.434192 0.489996 H 2.545588 3.966339 2.877907 H 1.925779 2.358118 2.508320 H 0.909013 3.793657 2.253573 H 4.788627 2.238517 2.517533 H 5.762263 1.648137 1.156655 H 4.202325 4.320632 2.619899 H 6.130108 2.500239 1.253607 H 5.128781 2.036399 2.635263 H 5.129404 1.046110 1.165246 H 1.526306 6.054960 2.622508 H 3.206931 6.593221 2.579824 H 2.088315 7.061769 1.285596 N 0.280308 3.080624 1.453653 O 1.348657 3.690700 1.424922 C 2.845646 4.383198 1.544225 H 2.490469 5.252896 0.992591 C 4.034049 4.670322 2.420838 H 4.546038 3.760779 2.748087 H 3.721148 5.211571 3.320988 O 4.949291 5.580449 1.783670

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214 C 5.870691 5.162064 0.865436 O 6.535650 5.998301 0.305101 C 1.415325 1.553494 3.191124 C 2.485080 1.915879 2.103952 C 1.128552 0.017648 1.336028 C 0.937664 0.122362 2.860983 H 1.831623 1.628184 4.200475 H 1.573991 0.613055 3.363270 C 2.50 0286 0.695540 1.132520 H 2.680351 0.975775 0.088377 C 2.191332 3.221440 1.411412 C 0.015668 0.682169 0.548735 H 3.476317 1.953732 2.561530 H 1.208379 1.059088 1.022142 H 1.326048 3.212634 0. 747956 H 0.570751 1.399136 1.115249 H 0.093989 0.060246 3.182557 H 0.581122 2.260446 3.145403 O 3.588300 0.118496 1.594597 C 4.255028 0.957298 0.737001 C 3.670529 1.607761 0.353462 C 5.607261 1.174961 1.043247 C 4.446449 2.462205 1.139086 H 2.613617 1.519927 0.569806 C 6.371333 2.024031 0.254836 H 6.035223 0.668788 1.902764 C 5.794847 2.667761 0.848022 H 3.973772 2.991081 1.95892 5 H 7.416488 2.192387 0.495029 C 6.648635 3.537899 1.723252 F 7.379839 2.805861 2.602238 F 7.538672 4.259200 0.999246 F 5.919259 4.408098 2.452489 C 6.023549 3.672188 0.626019 H 6.369268 3. 160516 1.531958 H 5.076754 3.212870 0.325453 H 6.764535 3.532722 0.161273 C 0.001506 0.846585 0.827232 C 1.808026 0.536780 1.942159 H 0.731436 0.356826 1.461261 H 0.554931 1.668088 1.269455 H 1.232774 1.241223 2.555182 C 2.620834 0.411831 2.746040 H 3.635499 0.005689 2.861588 H 2.709416 1.398754 2.292038 O 2.017639 0.541776 4.056451 C 2.710015 1.277620 4.955240 O 3.769445 1.816442 4.707333 C 1.993364 1.324650 6.283190 H 0.980024 1.718134 6.153600 H 1.899283 0.313014 6.691773 H 2.553043 1.953400 6.976407 TS27* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8213705100 a.u. M06/SD D/6 311++G(d,p) SCF energy in solution: 2907.8582077400 a.u Ru 1.119975 1.192644 0.361909 O 1.542868 0.098201 2.214938 O 0.649781 1.937424 1.377569 N 3.220800 2.275737 1.330644 N 3.800127 0.172812 1.177891 C 2.882774 1.096299 0.744855 C 4.331674 2.189791 2.283753 C 2.315390 3.425449 1.284819 C 1.474810 3.506789 2.588150 C 0.455696 4.657389 2.490555 C 1.211644 5.986414 2.286000 C 2.045198 5.91 0346 0.989780 C 3.075474 4.762758 1.107716 C 1.101475 5.652679 0.203365 C 0.346709 4.312482 0.003650 C 1.391288 3.187256 0.086932 C 0.480160 4.394050 1.295131 C 4.082168 1.147037 0.684593 C 3.577828 2.271262 1.368649 C 3.885398 3.545811 0.878300 C 2.802055 2.152538 2.660950 C 4.827727 0.755781 2.070138 C 4.994440 1.306301 0.381262 C 4.711832 3.733336 0.233787 C 5.272864 2.601364 0.832766 C 5.717199 0.139332 1.020905 C 4.992786 5.117515 0.769504 H 2.023783 3.232604 0.842384 H 5.097732 2.940525 2.067729 H 3.974332 2.356572 3.306992 H 0.959034 2.550562 2.736934 H 2.13 5431 3.665684 3.452092 H 0.125677 4.702555 3.421117 H 1.864354 6.188556 3.147355 H 0.498203 6.818726 2.223523 H 2.584335 6.855102 0.841837 H 3.701479 4.712022 0.206628 H 3.742810 4.953457 1. 961053 H 1.672574 5.626916 1.141813 H 0.382040 6.478397 0.292816 H 0.315736 4.127388 0.850717 H 1.036808 3.460549 1.444827 H 1.222682 5.199340 1.213871 H 3.483666 4.415098 1.395655 H 3.448268 2.404322 3.512839 H 2.423387 1.141783 2.825012 H 1.958297 2.849665 2.687017 H 4.892953 0.178533 2.998025 H 5.808398 0.722601 1.583187 H 5.945733 2.721057 1.678860 H 6.732729 0.051657 0.611158 H 5.806411 0.285638 2.100664

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215 H 5.207179 0.812218 0.851214 H 4.241117 5.411867 1.513791 H 5.970949 5.166534 1.258814 H 4.971244 5.868633 0.027141 N 1.541283 1.348490 2.132245 O 2.35231 1 2.059291 2.718044 C 0.799389 4.579304 1.750742 H 0.016585 5.203920 1.321667 C 1.818001 5.352220 2.544327 H 2.741240 4.788618 2.708729 H 1.414646 5.612489 3.529627 O 2.090401 6.630984 1.944 481 C 2.954462 6.774721 0.894712 O 3.059091 7.865863 0.391288 C 1.107274 1.329030 3.235474 C 1.701498 2.214475 2.082062 C 1.248697 0.075975 1.215119 C 1.244962 0.141772 2.773850 H 1.632976 1.506262 4.178629 H 2.201180 0.559887 3.100406 C 2.149746 1.183676 1.008588 H 2.144272 1.570949 0.014019 C 0.746383 3.253937 1.557948 C 0.209841 0.004655 0.787623 H 2.612501 2.704409 2.432840 H 1.729481 0.943203 0.758167 H 0.091250 2.878761 0.972230 H 0.788109 0.684412 1.409730 H 0.450580 0.781989 3.170808 H 0.058178 1.587637 3.410494 O 3.490789 0.868631 1.424275 C 4.421209 0.250 472 0.631644 C 4.275013 0.019599 0.729851 C 5.611971 0.093149 1.293632 C 5.317125 0.642189 1.420279 H 3.366401 0.224194 1.265570 C 6.645721 0.699737 0.595169 H 5.702324 0.125817 2.352983 C 6.503207 0.981490 0.770225 H 5.179453 0.877551 2.469821 H 7.562329 0.968160 1.110977 C 7.645428 1.593993 1.525258 F 8.552022 0.662400 1.916785 F 8.325973 2.490212 0.769396 F 7.238414 2.233388 2.642543 C 3.747311 5.563377 0.443531 H 4.417877 5.211501 1.236299 H 3.090409 4.731794 0.169512 H 4.345715 5.855983 0.419372 C 0.929263 1.074518 1.119030 C 1.367162 0.139032 2.083283 H 0.095407 1.416586 1.183859 H 1.649147 1.729835 0.637669 H 0.604851 0.196404 2.780396 C 2.742402 0.196912 2.690389 H 3.118958 0.789185 2.981466 H 3.462454 0.673167 2.033290 O 2.609966 0.996535 3.900835 C 3.750068 1.275668 4.563990 O 4.853507 0.925066 4.195402 C 3.464716 2.069279 5.818042 H 2.894373 2.971531 5.575676 H 2.853324 1.473224 6.503920 H 4.405034 2.337187 6.301147 15* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8481204900 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8892070400 a.u Ru 1.540785 0.944467 0.228528 O 0.960287 3.088711 2.312878 O 0.157603 2.216293 0.626282 N 4.188217 0.749868 0.932832 N 3.755992 1.345611 0.491305 C 3.257871 0.076767 0.378370 C 5.285985 0.049162 1.607451 C 3.831198 2.136370 1.238984 C 3.233507 2.240885 2.669464 C 2.767054 3.682037 2.948819 C 3.974347 4.634538 2.825737 C 4.565005 4.537559 1.403588 C 5.043611 3.091569 1.139652 C 3.481536 4.923479 0.376994 C 2.268816 3.961898 0.496490 C 2.772588 2.539452 0.200734 C 1.685 829 4.064757 1.919985 C 3.262008 2.586297 0.038229 C 2.481159 3.424874 0.784213 C 2.029314 4.640475 0.259718 C 2.212527 3.106961 2.238114 C 5.117155 1.374366 1.072143 C 3.694466 3.024703 1.3 06923 C 2.370217 5.064577 1.029439 C 3.220081 4.252566 1.784926 C 4.674369 2.239739 2.152241 C 1.834935 6.362849 1.586393 H 3.228686 2.513719 0.809326 H 6.255406 0.485903 1.353683 H 5.163253 0.097866 2.697624 H 2.389654 1.542825 2.755435 H 3.984397 1.938768 3.413058 H 2.354969 3.736194 3.965038 H 4.737624 4.378349 3.574285 H 3.660502 5.666550 3.030222 H 5.422948 5.216065 1.312648 H 5.494367 3.009787 0.141743 H 5.815354 2.816894 1.873470 H 3.888028 4.887366 0.642319 H 3.151914 5.956737 0.552460

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216 H 1.520506 4.253035 0.240182 H 0.811740 3.408525 2.018326 H 1.336354 5.089345 2.104886 H 1.414436 5.283385 0.886699 H 2.977012 3.573161 2.875397 H 2.229482 2.035080 2.445058 H 1.245625 3.508042 2.557263 H 5.183687 2.141511 1.848807 H 5.850062 1.613301 0.292221 H 3.520693 4.571460 2.780050 H 5.686187 2.654154 2.047351 H 4.398544 2.297144 3.208732 H 4.714847 1.184795 1.869256 H 0.857335 6.213914 2.063687 H 2.505889 6.780202 2.343959 H 1.699682 7.11 2277 0.799215 N 0.106632 3.017663 1.675545 O 1.123023 3.646158 1.957114 C 2.392731 4.186908 2.027107 H 1.994518 5.074791 1.537107 C 3.553169 4.473013 2.940734 H 4.109342 3.570856 3.210987 H 3.201435 4.932429 3.871480 O 4.424892 5.472964 2.381609 C 5.380956 5.169655 1.454058 O 5.999273 6.078272 0.956277 C 1.093792 1.141878 3.400604 C 2.167652 1.665645 2.386989 C 0.991798 0.306244 1.424580 C 0.759264 0.296746 2.952510 H 1.464020 1.182762 4.429783 H 1.450582 1.006321 3.419212 C 2.291325 0.541326 1.314037 H 2.476586 0.937914 0.309512 C 1.809009 3.003363 1.795020 C 0.22 3547 0.278180 0.681667 H 3.140725 1.726928 2.880076 H 1.187150 1.314430 1.059123 H 0.953180 3.000330 1.118570 H 0.688382 1.079378 1.255767 H 0.257671 0.598589 3.226977 H 0.202014 1.776069 3. 364735 O 3.443244 0.217431 1.721207 C 4.099609 1.043897 0.849161 C 3.563678 1.560249 0.335970 C 5.404119 1.392454 1.235625 C 4.335716 2.415136 1.124949 H 2.540800 1.367500 0.631241 C 6.165696 2.237084 0.441107 H 5.796567 0.988450 2.163483 C 5.635884 2.751954 0.749509 H 3.894174 2.841253 2.018995 H 7.172206 2.505148 0.746237 C 6.487316 3.619458 1.628866 F 7.274649 2.884449 2.455429 F 7.323863 4.402716 0.905513 F 5.750629 4.431805 2.416194 C 5.631126 3.709713 1.127490 H 5.995716 3.165678 2.006751 H 4.720619 3.210284 0.781906 H 6.390882 3.665942 0.346939 C 0.05962 0 0.752414 0.837480 C 0.900171 0.044237 1.902726 H 0.986672 0.606994 1.112053 H 0.337653 1.807179 0.893779 H 0.275295 0.739945 2.461491 C 1.742032 0.747740 2.861316 H 2.498125 0.115211 3.337 024 H 2.226430 1.596598 2.389932 O 0.846751 1.244551 3.898681 C 1.405420 2.028106 4.843983 O 2.576496 2.351117 4.851338 C 0.386161 2.432047 5.884090 H 0.484161 2.894126 5.407578 H 0.031336 1.544354 6.418761 H 0.841865 3.127551 6.589778 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8537842400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8914697400 a.u Ru 2.067836 0.406496 0.710964 O 2.303691 2.872523 0.547531 O 1.544093 1.815110 2.289110 N 4.141768 1.043282 0.680294 N 2.319766 1.597335 1.779138 C 2.803317 0.820631 0.750492 C 4.659961 1.989102 1.671328 C 4.988912 0.091081 0.042558 C 5.536182 0.979960 0.940166 C 6.360554 2.032688 0.175846 C 7.531708 1.339820 0.549030 C 6.977258 0.293099 1.536831 C 6.180180 0.775665 0.755163 C 6.056630 0.992712 2.559925 C 4.870365 1.678 459 1.823441 C 4.095454 0.572506 1.094538 C 5.441861 2.727524 0.846314 C 1.128448 1.390496 2.562991 C 1.077524 0.270585 3.429058 C 0.039632 0.104890 4.248105 C 2.193478 0.747014 3.471776 C 3.390392 2.378786 2.446271 C 0.104327 2.352932 2.580366 C 1.093404 1.028994 4.261218 C 0.995368 2.141504 3.427090 C 0.123727 3.601582 1.728676 C 2.273453 0.841040 5.186519 H 3.818042 0.203232 1.850938

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217 H 5.125451 2.849197 1.178756 H 5.413578 1.518048 2.312546 H 4.691466 1.457947 1.450830 H 6.159934 0.499811 1.706942 H 6.750148 2.770756 0.889075 H 8.199654 0.856898 0.178513 H 8.132275 2.083610 1.088973 H 7.807172 0.196967 2.062147 H 5.804583 1.553130 1.433703 H 6.837372 1.269161 0.024430 H 5.680051 0.266357 3.292952 H 6.626534 1.745559 3.121516 H 4.226007 2.162918 2.563660 H 4.625551 3.248362 0.338302 H 6.008373 3.480018 1.411610 H 0.081481 0.759515 4.907809 H 3.169293 0.280485 3.652459 H 2.272849 1.296810 2.527364 H 2.020950 1.473158 4.271656 H 3.442 223 2.110574 3.507088 H 3.173860 3.449878 2.381827 H 1.789619 2.885155 3.437161 H 0.328809 4.438919 2.270034 H 0.459912 3.463481 0.810615 H 1.129139 3.899703 1.427041 H 2.674989 0.177343 5.1 25149 H 3.082985 1.539287 4.952010 H 1.986537 1.008138 6.232755 N 1.831563 2.948713 1.723267 O 1.640069 4.006830 2.302088 C 5.070001 3.723288 1.430251 H 5.930430 3.557186 2.077054 C 5.296292 4.787413 0.391359 H 4.538585 4.778703 0.396531 H 5.276303 5.779819 0.856117 O 6.623800 4.695198 0.157850 C 6.923185 3.875020 1.207914 O 8.081938 3.753210 1.522394 C 1.464312 3.613468 1.777961 C 2.642082 3.102235 0.920986 C 0.612573 2.005708 0.059637 C 0.192079 3.168243 1.014544 H 1.511996 4.694858 1.938667 H 0.226241 3.991989 0.433179 C 2.097968 1.738219 0.456872 H 2.124352 1.0 35088 1.296128 C 3.950686 3.022637 1.651292 C 0.239451 0.745715 0.179757 H 2.730868 3.734393 0.028755 H 0.629258 2.357328 0.977423 H 3.961711 2.317384 2.485445 H 0.206833 0.391597 1.207810 H 0.596269 2.849495 1.701811 H 1.509278 3.141621 2.769129 O 2.861043 1.222901 0.642767 C 3.461410 0.001767 0.609223 C 3.767196 0.726363 0.552235 C 3.800056 0.535044 1.863954 C 4.358205 1.984342 0.445329 H 3.558752 0.326377 1.536781 C 4.392722 1.786633 1.959509 H 3.572595 0.045950 2.751896 C 4.664470 2.527766 0.803435 H 4.592236 2.541569 1.346997 H 4.642240 2.192702 2.934127 C 5.2 06357 3.921157 0.902731 F 6.005652 4.234432 0.141207 F 5.913721 4.117180 2.035342 F 4.207523 4.850177 0.905618 C 5.782077 3.202136 1.946502 H 5.150840 3.947798 2.445139 H 5.140436 2.615795 1 .282256 H 6.216789 2.549488 2.704029 C 0.131134 0.407467 0.828621 C 1.072187 1.034388 1.656025 H 0.848372 0.014997 1.548836 H 0.576915 1.219090 0.248918 H 0.985671 0.760052 2.714274 C 1.308330 2.510289 1.500883 H 2.191556 2.819265 2.071774 H 1.457916 2.802974 0.463633 O 0.156786 3.232565 2.025942 C 0.204877 4.580228 1.911391 O 1.125976 5.174069 1.389341 C 1.027498 5.222140 2.5059 52 H 1.924560 4.910685 1.960670 H 1.152606 4.905635 3.546552 H 0.928341 6.307317 2.457104 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8418655000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8830652200 a.u Ru 1.917759 0.866156 0.131380 O 0.812622 2.751934 1.358203 O 0.919450 2.791126 0.014344 N 4.436572 0.250271 0.744553 N 3.425572 2.020181 0.039494 C 3.292979 0.669645 0.132388 C 5.325890 1.336465 1.167140 C 4.529713 1.104422 1.288677 C 4.104354 1.132415 2.783441 C 4.118347 2.580787 3.310676 C 5.541134 3.159077 3.167199 C 5.960757 3.138266 1.682327 C 5.960876 1.680501 1.170069 C 4.964107 3.979056 0.858948 C 3.532580 3.398699 0.999703 C 3.557260 1.957920 0.466538

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218 C 3.124306 3.421421 2.486360 C 2.565302 2.952872 0.710024 C 1.622341 3.678358 0.048520 C 0.795915 4.591 203 0.613523 C 1.574656 3.578848 1.556693 C 4.740787 2.529497 0.407575 C 2.782910 3.256098 2.068585 C 0.914495 4.836331 1.987566 C 1.929019 4.178641 2.687557 C 3.938043 2.678958 2.859167 C 0.021150 5.793518 2.687727 H 3.896610 1.966370 0.596295 H 6.364574 1.129965 0.895929 H 5.277653 1.474473 2.255463 H 3.097926 0.701646 2.877779 H 4.785500 0.507964 3.378363 H 3.824671 2.579926 4.368604 H 6.251531 2.576826 3.771240 H 5.566907 4.188322 3.548295 H 6.972754 3.550345 1.578215 H 6.286825 1.638627 0.122072 H 6.670354 1.081465 1.759081 H 5.263358 3.996140 0.198163 H 4.97 4883 5.020446 1.208394 H 2.827199 3.993712 0.419031 H 2.104316 3.033642 2.596482 H 3.112954 4.456821 2.851917 H 0.058669 5.145588 0.036111 H 2.320730 4.250991 2.003713 H 1.794267 2.571971 1. 919165 H 0.598718 3.880922 1.945598 H 4.613358 3.418700 1.031446 H 5.348557 2.807716 0.461611 H 2.070794 4.385767 3.745804 H 4.762641 3.403623 2.901805 H 3.636537 2.456616 3.886309 H 4.327184 1.758813 2.415664 H 0.945396 5.287084 2.995878 H 0.436300 6.212775 3.589483 H 0.310352 6.623364 2.033909 N 0.008531 3.418078 0.693675 O 0.009585 4.644431 0.649973 C 2.714431 3.737166 2.25440 0 H 2.554891 4.685796 1.742648 C 3.683452 3.827482 3.401167 H 4.039021 2.846368 3.729767 H 3.209907 4.309415 4.263982 O 4.782876 4.702377 3.088855 C 5.861957 4.285873 2.361326 O 6.690313 5. 106837 2.052366 C 0.849833 0.869029 3.271664 C 2.096042 1.262815 2.409337 C 0.823133 0.582674 1.309690 C 0.477983 0.556271 2.815759 H 1.072780 0.926332 4.341903 H 1.101918 1.291734 3.335076 C 2.192199 0.161994 1.305365 H 2.465004 0.569399 0.324926 C 2.039364 2.655537 1.841425 C 0.262611 0.123661 0.488326 H 2.996199 1.151907 3.018953 H 0.959724 1.596764 0.937968 H 1.358542 2.790603 1.000196 H 0.483138 1.114742 0.885312 H 0.568780 0.810165 3.013402 H 0.023930 1.563975 3.086949 O 3.246977 0.707768 1.759143 C 4.052476 1.379771 0.882575 C 3.701656 1.714886 0.428914 C 5.304215 1.761419 1.391586 C 4.610064 2.411940 1.225920 H 2.714856 1.502701 0.817616 C 6.200771 2.455037 0.590741 H 5.550209 1.503173 2.416707 C 5.860871 2.779194 0.728906 H 4.323357 2.692 204 2.233814 H 7.166419 2.749714 0.988991 C 6.858114 3.471108 1.610588 F 7.694746 2.590655 2.217051 F 7.643853 4.324275 0.912192 F 6.264062 4.180154 2.595816 C 5.971736 2.813956 2.012499 H 6.070407 2.201548 2.916548 H 5.092913 2.459610 1.465088 H 6.862718 2.680238 1.398770 C 0.082114 0.206311 1.084827 C 1.140375 0.596526 1.948167 H 0.877519 0.253277 1.323962 H 0.121152 1.255309 1.384250 H 0.712328 1.542173 2.283639 C 1.753554 0.141451 3.106583 H 2.674758 0.341674 3.450324 H 1.961205 1.183161 2.881291 O 0.782857 0.088712 4.191026 C 1.088529 0.781523 5.307038 O 2.096954 1.446459 5.437200 C 0.018636 0.608532 6.360094 H 0.959589 0.891222 5.958357 H 0.044481 0.443903 6.656505 H 0.259494 1.222500 7.228620 TS20E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.836039990 0 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8652953700 a.u Ru 1.649798 0.806814 0.175737 O 0.427279 2.591305 0.562949 O 2.238473 2.661888 1.752583 N 4.004299 0.275613 1.164524

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219 N 3.228890 1.987453 0.049802 C 3.020082 0.660610 0.307544 C 4.827097 1.379304 1.664138 C 3.928877 1.031995 1.817125 C 3.222276 0.921730 3.190027 C 3.040536 2.325597 3.799428 C 4.427805 2.969450 3.999316 C 5.1 44829 3.077638 2.637303 C 5.325868 1.662477 2.038930 C 4.297472 3.952048 1.688577 C 2.906525 3.299241 1.474677 C 3.132199 1.911538 0.842303 C 2.197535 3.190684 2.839542 C 2.574500 2.863361 0.881770 C 1.590387 3.749243 0.394766 C 0.973731 4.628168 1.290263 C 1.242298 3.817416 1.075185 C 4.456626 2.504292 0.694168 C 3.012860 2.929842 2.219312 C 1.348806 4.680165 2.638777 C 2.37979 8 3.843067 3.073409 C 4.107759 2.039665 2.764700 C 0.655208 5.621618 3.595959 H 3.777704 2.053210 0.039398 H 5.891336 1.129604 1.636982 H 4.559950 1.623040 2.701670 H 2.252779 0.432426 3.047 533 H 3.812411 0.292091 3.871456 H 2.531573 2.238150 4.769231 H 5.026983 2.368438 4.698375 H 4.320362 3.966924 4.446321 H 6.134077 3.532904 2.776860 H 5.860032 1.714332 1.081205 H 5.933093 1.050762 2.722904 H 4.805475 4.071970 0.722953 H 4.182684 4.957844 2.117299 H 2.315213 3.934225 0.807889 H 1.198890 2.757925 2.711861 H 2.057969 4.192636 3.268823 H 0.195742 5.290424 0.917018 H 0.385746 4.476171 1.235391 H 2.079303 4.224835 1.658734 H 1.020743 2.833772 1.500150 H 4.257912 3.457850 1.190978 H 5.232534 2.672953 0.063154 H 2.708327 3.896729 4.109557 H 4.804872 1.709 905 1.990391 H 4.679704 2.569786 3.533484 H 3.699482 1.134724 3.230693 H 0.265041 5.173133 3.993388 H 1.293882 5.866964 4.450911 H 0.370174 6.556345 3.101495 N 1.162267 3.237645 1.411574 O 0.806092 4.319756 1.860529 C 4.135510 2.678384 1.779954 H 5.002877 2.184402 2.220384 C 4.426853 4.037120 1.200582 H 5.079738 3.941958 0.324542 H 4.965280 4.660264 1.924121 O 3.259155 4.709463 0.712020 C 2.511252 5.523926 1.503767 O 1.498146 5.998272 1.041584 C 2.988181 5.810606 2.914512 H 3.923623 6.381852 2.906694 H 3.161113 4.886795 3.475946 H 2.220315 6.403445 3.411695 C 1.561639 0.644656 3.370637 C 2.699666 0.676254 2.310988 C 0.825864 0.849823 1.572117 C 0.806350 0.669680 3.118848 H 1.954290 0.720134 4.389835 H 1.349740 1.511463 3.563983 C 2.266753 0.369500 1.221034 H 2.347636 0.035253 0.209850 C 2.954572 2.052842 1.756796 C 0.308941 0.065248 0.934074 H 3.625733 0.296742 2.756386 H 0.748565 1.899624 1.285168 H 2.101857 2.557049 1.300373 H 0.31 3066 0.988154 1.240657 H 0.200620 0.668511 3.542892 H 0.892788 1.502987 3.227167 O 3.072913 1.555894 1.309125 C 4.285097 1.625665 0.693899 C 4.933564 0.552986 0.067492 C 4.894702 2.892107 0. 712849 C 6.176919 0.755973 0.534633 H 4.491977 0.436061 0.054934 C 6.131345 3.080252 0.115030 H 4.369934 3.712134 1.191868 C 6.782675 2.011124 0.516324 H 6.674251 0.074466 1.025130 H 6.590760 4.063525 0.123378 C 8.145336 2.212155 1.110593 F 9.124977 2.123682 0.176296 F 8.270716 3.431812 1.681941 F 8.429080 1.288540 2.057472 C 0.163530 0.316427 1.250117 C 0.957764 0.191225 2.08747 1 H 0.423207 1.300327 0.872241 H 0.980614 0.391939 1.354213 H 1.556527 1.080010 2.228086 C 0.912089 0.665293 3.334081 H 0.508275 1.660823 3.153258 H 0.261546 0.168451 4.070527 O 2.237066 0. 703128 3.875956 C 2.669805 1.677233 4.729161 O 3.794818 1.588604 5.158900

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220 C 1.718300 2.801914 5.077644 H 1.550136 3.441575 4.204164 H 0.746946 2.429481 5.421446 H 2.177848 3.394909 5.869069 TS21E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8241436100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8603766000 a.u Ru 2.171037 0.751984 0.071798 O 1.113124 2.609887 0.195294 O 2.529733 4.107795 0.595501 N 4.311948 1.009422 0.735658 N 3.147209 2.228599 0.659328 C 3.201567 1.009448 0.045455 C 4.939984 2.326616 0.861934 C 4.506192 0.120250 1.648339 C 3.686512 0.087645 2.950991 C 3.803197 1.152492 3.857157 C 5.287629 1.371015 4.216301 C 6.105294 1.578428 2.924647 C 5.987464 0.322194 2.030603 C 5.556786 2.809512 2.174535 C 4.067422 2.588761 1.801739 C 3.983615 1.356944 0.875675 C 3.258300 2.379636 3.097747 C 2.096231 2.786639 1.463442 C 1.082330 3.526675 0.811710 C 0.057596 4.087521 1.577051 C 1.114842 3.764839 0.682837 C 4.327258 3.062905 0.337336 C 2.130252 2.69 7753 2.866919 C 0.028348 3.952722 2.972154 C 1.073260 3.267234 3.592671 C 3.268821 2.059926 3.632615 C 1.079866 4.585546 3.781493 H 4.679321 1.524612 0.043607 H 6.029197 2.260103 0.804344 H 4.673711 2.799137 1.818838 H 2.633527 0.267924 2.686211 H 4.040299 0.984145 3.481179 H 3.221779 0.988100 4.774452 H 5.673202 0.507907 4.777940 H 5.390427 2.248229 4.868808 H 7.161887 1.735008 3.178727 H 6.589835 0.442266 1.120008 H 6.378146 0.553307 2.571180 H 6.145348 2.996177 1.266107 H 5.657160 3.702856 2.807184 H 3.709881 3.472038 1.270636 H 2.194832 2.242369 2.861734 H 3.32 6608 3.273217 3.732809 H 0.719916 4.659161 1.075291 H 0.223960 4.312227 1.000781 H 1.983870 4.371214 0.970613 H 1.182770 2.834308 1.257779 H 4.027268 4.088676 0.109812 H 5.010379 3.089212 1. 196739 H 1.084346 3.180344 4.677612 H 4.069774 1.714378 2.974894 H 3.701615 2.783312 4.334495 H 2.925430 1.204731 4.226296 H 2.028015 4.575165 3.233996 H 1.226652 4.068383 4.735350 H 0.850558 5.635183 4.008878 N 1.524010 3.857948 0.092004 O 0.861661 4.713421 0.675294 C 4.369658 2.690061 1.485151 H 5.152670 2.189803 2.056429 C 4.756194 4.035934 0.928317 H 5.432985 3.924599 0.073140 H 5.293296 4.627306 1.679153 O 3.635939 4.765751 0.406810 C 2.821129 5.490791 1.218904 O 1.784036 5.913545 0.757914 C 3.260742 5.758393 2.644498 H 4.198022 6.325673 2.670595 H 3.4159 81 4.823974 3.193596 H 2.479321 6.341474 3.131986 C 1.513183 0.841612 2.757782 C 2.795479 0.757846 1.874550 C 0.960442 0.683926 0.941582 C 0.713380 0.434078 2.444334 H 1.758406 0.945682 3.81 9707 H 1.111738 1.282982 3.010793 C 2.465974 0.326447 0.785924 H 2.707631 0.003609 0.230338 C 3.185859 2.094959 1.306834 C 0.097022 0.163532 0.019664 H 3.627449 0.367707 2.470427 H 0.824893 1.733558 0.679966 H 2.425668 2.607659 0.716522 H 0.114665 1.181431 0.337558 H 0.347496 0.343377 2.701361 H 0.932191 1.731604 2.481141 O 3.168455 1.548970 1.062394 C 4.477749 1.691868 0.721914 C 5.273771 0.693330 0.144189 C 5.029736 2.958845 0.979658 C 6.605379 0.969698 0.170435 H 4.874861 0.293906 0.054229 C 6.354681 3.220258 0.665234 H 4.393081 3.720894 1.417216 C 7.154390 2.22 5284 0.085335 H 7.217939 0.197533 0.624520 H 6.771048 4.203799 0.858052 C 8.602344 2.495934 0.197072 F 9.380143 2.296201 0.896667 F 8.810226 3.774708 0.586241

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221 F 9.090096 1.690592 1.169084 C 0.073277 0.122973 1.313141 C 2.534575 0.945236 1.864824 H 0.378099 0.640655 2.018725 H 0.304641 1.054016 1.727142 H 3.025901 0.158809 2.444151 C 2.262249 2.142919 2.727029 H 3.140972 2.800531 2.681326 H 1.402908 2.724143 2.391237 O 2.059717 1.645901 4.069457 C 1.919227 2.489186 5.133671 O 1.755872 2.006885 6.228447 C 1.980308 3.979765 4.866713 H 2.951632 4.269853 4.450681 H 1.21 7363 4.291570 4.145297 H 1.822978 4.501074 5.811128 TS22E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8311707400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8630028300 a.u Ru 1.786012 0.680440 0.077510 O 1.264307 2.483370 1.193117 O 2.760992 3.527603 0.030265 N 3.788542 1.355896 0.402194 N 2.180470 1.975212 1.744249 C 2.536183 1.039434 0.805817 C 4.398704 2.477598 1.118291 C 4.401402 0.692949 0.747836 C 4.227584 1.577621 2.010119 C 4.777568 0.844595 3.247647 C 6.273170 0.533413 3.033513 C 6.441637 0.352717 1.781513 C 5.908083 0.402344 0.540403 C 5.658978 1.667569 1.984233 C 4.152 362 1.354996 2.182452 C 3.657885 0.636450 0.916661 C 3.988978 0.466586 3.432382 C 0.900764 2.206636 2.350095 C 0.093093 2.920666 1.647143 C 1.337671 3.124899 2.256893 C 0.181714 3.585927 0.3 15244 C 3.212331 3.019755 1.927264 C 0.701912 1.856493 3.702900 C 1.597677 2.685578 3.558911 C 0.556482 2.081707 4.272012 C 1.830375 1.343025 4.571603 C 2.958836 2.881242 4.184948 H 3.933951 1.272557 0.039328 H 5.213977 2.122594 1.759491 H 4.808360 3.218167 0.423779 H 3.160491 1.799460 2.140416 H 4.750472 2.535248 1.871461 H 4.655395 1.484175 4.132354 H 6.841925 1.467550 2.919433 H 6.678874 0.017738 3.914367 H 7.505518 0.575452 1.627800 H 6.041727 0.200807 0.366303 H 6.474529 1.336168 0.406731 H 5.790065 2.330450 1.119844 H 6.052330 2.200698 2.861391 H 3.604936 2.2 88839 2.328284 H 2.927193 0.249386 3.604609 H 4.354808 1.003044 4.318706 H 2.105061 3.673995 1.714259 H 0.729630 3.657813 0.286150 H 0.521931 4.617808 0.478708 H 0.952374 3.077422 0.267602 H 2.843614 3.979792 1.543613 H 3.446971 3.146795 2.987815 H 0.718663 1.793981 5.309137 H 2.557477 0.746721 4.016768 H 2.371056 2.186744 5.023051 H 1.444252 0.739911 5.400297 H 3.500927 3.703895 3.708251 H 3.575416 1.978535 4.079804 H 2.881037 3.095522 5.256593 N 1.932796 3.571622 0.911568 O 1.716559 4.578845 1.577709 C 4.615664 2.395022 2.500696 H 5.068533 1.943154 3.383902 C 5.4 75456 3.412302 1.796813 H 6.376888 2.938049 1.391514 H 5.814554 4.190125 2.492222 O 4.823409 3.987775 0.656925 C 3.953254 5.027269 0.776583 O 3.247741 5.295809 0.169569 C 3.934799 5.811623 2 .073545 H 4.912130 6.263309 2.277448 H 3.676184 5.168263 2.921007 H 3.189772 6.601535 1.977681 C 1.198146 1.637469 3.306279 C 2.507904 1.013782 2.764016 C 0.502542 0.347989 2.056964 C 0.211046 0.466058 3.353454 H 1.351152 2.119508 4.277847 H 0.422472 0.172743 4.219762 C 2.031599 0.130202 1.806029 H 2.219573 0.137795 0.760917 C 3.398623 2.021228 2.096535 C 0.336721 0.171449 0.9122 41 H 3.039929 0.527649 3.590829 H 0.311546 1.409516 2.211083 H 2.985400 2.482660 1.198702 H 0.041724 1.179174 0.598105 H 0.833516 0.782287 3.428208 H 0.838318 2.412473 2.616322 O 2.693452 1.370583 2.089770 C 3.762424 1.793917 1.357603

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222 C 4.550072 0.975640 0.535837 C 4.066576 3.160597 1.474761 C 5.620487 1.530607 0.165985 H 4.357578 0.087535 0.458458 C 5.139140 3.699631 0.778430 H 3.438307 3.778535 2.107924 C 5.921881 2.888092 0.053230 H 6.224244 0.896065 0.806969 H 5.361024 4.758286 0.864759 C 7.110811 3.458939 0.767967 F 8.242492 3.373704 0.024898 F 6.942694 4.76 7326 1.065336 F 7.363739 2.808077 1.927939 C 0.310739 0.991133 1.124425 C 0.742938 1.796571 1.562907 H 1.057093 1.421711 0.466781 H 0.600110 0.099259 1.672116 H 0.778129 2.810675 1.179225 C 1.398640 1.604577 2.909973 H 1.006485 0.712941 3.395272 H 1.178004 2.465469 3.550040 O 2.823128 1.390005 2.839658 C 3.760823 2.384567 2.893595 O 4.913189 2.069256 2.709602 C 3.312032 3.798457 3.188961 H 2.716109 3.861234 4.105738 H 2.722483 4.184994 2.351512 H 4.206284 4.412402 3.300091 TS23E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8241754400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8 602309900 a.u Ru 2.170533 0.748690 0.067739 O 1.114981 2.607718 0.199030 O 2.535047 4.105956 0.584833 N 4.301212 1.020759 0.749749 N 3.137129 2.236368 0.648593 C 3.195045 1.016107 0.037537 C 4. 919539 2.341850 0.883371 C 4.497138 0.109354 1.661505 C 3.673464 0.093793 2.962306 C 3.792735 1.146985 3.867256 C 5.277070 1.360055 4.230005 C 6.098836 1.562815 2.940207 C 5.978265 0.306009 2.047330 C 5.557106 2.795225 2.187370 C 4.067923 2.579826 1.810760 C 3.982034 1.347363 0.885694 C 3.254627 2.375322 3.104986 C 2.096143 2.782376 1.473559 C 1.067867 3.522654 0.843856 C 0.054520 4.074544 1.629812 C 1.079619 3.777042 0.648330 C 4.310494 3.076695 0.318501 C 2.156672 2.688354 2.875275 C 0.048879 3.928942 3.024838 C 1.111024 3.251166 3.623034 C 3.314921 2.058574 3.617852 C 1.075407 4.506950 3.852120 H 4.681487 1.511262 0.056051 H 6.009575 2.282889 0.833801 H 4.642777 2.810441 1.839214 H 2.620443 0.270542 2.695407 H 4.022623 0.990880 3.494562 H 3.208 286 0.986037 4.783235 H 5.657777 0.496093 4.793654 H 5.381612 2.237610 4.881774 H 7.155395 1.715491 3.196787 H 6.583280 0.422611 1.138041 H 6.364256 0.570365 2.589864 H 6.148891 2.978621 1.2 80371 H 5.659217 3.688814 2.819388 H 3.715088 3.463851 1.277709 H 2.191243 2.242058 2.866474 H 3.324938 3.269389 3.739135 H 0.731677 4.649170 1.145021 H 0.178792 4.317090 0.950089 H 1.937749 4.397378 0.939218 H 1.152733 2.853622 1.233848 H 4.003626 4.100502 0.091258 H 4.998710 3.107865 1.173664 H 1.146106 3.165898 4.707444 H 4.102679 1.713335 2.944215 H 3.760031 2.786801 4.306996 H 2.988029 1.204766 4.222718 H 1.967626 3.868912 3.805545 H 0.792519 4.599287 4.905557 H 1.369983 5.496813 3.486786 N 1.527523 3.855548 0.099803 O 0.864817 4.710322 0.683724 C 4.378857 2.6 83302 1.531977 H 5.151095 2.180328 2.115437 C 4.778137 4.029693 0.985913 H 5.484154 3.918511 0.154624 H 5.287680 4.624789 1.753005 O 3.673643 4.753324 0.424723 C 2.832728 5.484893 1.202902 O 1.812717 5.905783 0.703422 C 3.222549 5.761095 2.641257 H 4.158728 6.328094 2.696703 H 3.357940 4.830017 3.201209 H 2.425044 6.347566 3.097634 C 1.507702 0.836841 2.761639 C 2.795964 0.751881 1.887692 C 0.963604 0.685181 0.940638 C 0.710940 0.439140 2.443085 H 1.745501 0.942145 3.825144 H 1.108794 1.288627 3.009095

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223 C 2.469439 0.325002 0.790603 H 2.712531 0.012958 0.222748 C 3.197698 2.090238 1.331091 C 0.101651 0.162559 0.017755 H 3.620903 0.353752 2.488117 H 0.830523 1.734437 0.676363 H 2.448485 2.605694 0.729290 H 0.107995 1.181278 0.334349 H 0.350891 0.350812 2.696755 H 0.928547 1.726437 2.479733 O 3.172458 1.548997 1.058744 C 4.481596 1.689888 0.716632 C 5.278768 0.686500 0.149023 C 5.032031 2.960055 0.961575 C 6.609983 0.961353 0.168496 H 4.88 1245 0.303352 0.038863 C 6.356659 3.219924 0.644474 H 4.394452 3.725695 1.391457 C 7.157482 2.220176 0.074477 H 7.223484 0.185334 0.614705 H 6.771855 4.205835 0.827380 C 8.605179 2.489297 0. 210729 F 9.384036 2.295308 0.883287 F 8.812787 3.765896 0.607068 F 9.091937 1.678599 1.178806 C 0.072355 0.126725 1.313724 C 2.541394 0.943106 1.859010 H 0.378629 0.635366 2.020380 H 0.301686 1.059959 1.726301 H 3.031594 0.155796 2.437997 C 2.276436 2.143224 2.720138 H 3.155399 2.799912 2.666586 H 1.415424 2.724597 2.388705 O 2.082665 1.650043 4.065199 C 1.951412 2.496386 5.12815 9 O 1.795819 2.017308 6.225475 C 2.012374 3.986188 4.856779 H 2.981369 4.274076 4.433829 H 1.245232 4.296995 4.139405 H 1.861727 4.510173 5.800805 10E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.855 3599400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8919833900 a.u Ru 1.990753 0.664908 0.019441 O 1.188750 2.599862 0.551299 O 2.788992 3.625124 0.556350 N 4.119376 1.288611 0.316085 N 2.685668 2. 320398 0.968569 C 2.902240 1.162767 0.278834 C 4.694947 2.631316 0.206994 C 4.496268 0.315523 1.337557 C 3.970275 0.759320 2.730713 C 4.268913 0.324961 3.782900 C 5.793105 0.550561 3.854586 C 6.315570 0.994640 2.472264 C 6.024880 0.107587 1.428359 C 5.608783 2.301768 2.059397 C 4.074200 2.075826 1.980798 C 3.820874 0.996660 0.914227 C 3.562978 1.630133 3.365103 C 1.569047 2.71083 7 1.784221 C 0.530743 3.457153 1.187308 C 0.548350 3.860964 1.979899 C 0.602359 3.889150 0.261010 C 3.860206 3.220203 0.933714 C 1.584878 2.474877 3.172322 C 0.598289 3.571319 3.349923 C 0. 478726 2.891696 3.924630 C 2.767522 1.846191 3.878311 C 1.764062 4.035568 4.192290 H 4.244762 1.333700 0.054342 H 5.762084 2.592939 0.025604 H 4.565174 3.188870 1.145420 H 2.889014 0.938103 2.660722 H 4.442071 1.708664 3.021193 H 3.896950 0.007060 4.761319 H 6.297777 0.372383 4.173805 H 6.025429 1.317403 4.605409 H 7.399694 1.158607 2.522387 H 6.417040 0.179251 0.443856 H 6.525918 1.041034 1.724422 H 5.984088 2.653113 1.089599 H 5.826406 3.091357 2.791882 H 3.602508 3.015131 1.693516 H 2.474999 1.486790 3.338867 H 3.761467 2.418367 4.103756 H 1.350154 4.435199 1.520872 H 0.304504 4.429513 0.543502 H 1.448445 4.569950 0.424490 H 0.744335 3.048251 0.947420 H 3.549813 4.253463 0.758646 H 4.389392 3.176506 1.894203 H 0.471260 2.688176 4.993804 H 3.362 274 1.203088 3.225882 H 3.432648 2.625608 4.274715 H 2.442923 1.239862 4.729569 H 2.699933 4.014975 3.624417 H 1.888585 3.412215 5.083886 H 1.616439 5.069032 4.532924 N 1.803480 3.708362 0.2 08692 O 1.370842 4.766101 0.653966 C 4.527436 2.491453 1.756130 H 5.193717 1.974521 2.447921 C 5.122831 3.712916 1.106039 H 5.898892 3.428460 0.385703 H 5.606771 4.354882 1.851552 O 4.167658 4.454602 0.333841

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224 C 3.344968 5.371864 0.907817 O 2.433035 5.815832 0.245708 C 3.623437 5.812929 2.330893 H 4.606403 6.290541 2.412026 H 3.602353 4.963191 3.020955 H 2.855152 6.532099 2.615018 C 1.410972 1.128502 2.972541 C 2.703050 0.796605 2.173254 C 0.769486 0.632693 1.413348 C 0.540959 0.130921 2.856990 H 1.637703 1.409212 4.006637 H 0.892000 0.894945 3.561354 C 2.278481 0.3 34077 1.166408 H 2.476660 0.053079 0.125833 C 3.301926 2.012025 1.521405 C 0.143888 0.053901 0.395490 H 3.438442 0.348653 2.851343 H 0.624656 1.710572 1.342034 H 2.661491 2.535228 0.810342 H 0.069087 1.140860 0.444301 H 0.515025 0.057581 3.076731 H 0.901911 1.987303 2.515980 O 2.968712 1.563981 1.450821 C 4.208152 1.814941 0.951261 C 5.002597 0.893262 0.256795 C 4.687858 3.119080 1.170281 C 6.259856 1.280481 0.211312 H 4.664699 0.122596 0.094087 C 5.938839 3.490804 0.703436 H 4.052415 3.820977 1.700458 C 6.736279 2.572082 0.005407 H 6.871302 0.565631 0.752013 H 6.297569 4.502079 0.868388 C 8.108361 2.973889 0.446741 F 9.002731 2.963142 0.573365 F 8.124260 4.229126 0.952841 F 8.595868 2.146549 1.399731 C 0.038916 0.438908 1.109980 C 1.302565 0.717179 1.870758 H 0.531284 0.379249 1.645022 H 0.657193 1.340492 1.110677 H 1.591707 0.124158 2.490187 C 1.353119 1.977838 2.708714 H 1.262567 2.880409 2.109116 H 0.539146 1.959440 3.452524 O 2.61 0414 1.936411 3.402471 C 3.180437 3.045176 3.958753 O 4.227162 2.908827 4.546306 C 2.473642 4.373440 3.791243 H 2.504347 4.678450 2.739145 H 1.423854 4.323442 4.100499 H 2.996577 5.112541 4. 398936 11E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8490425700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8846568900 a.u Ru 2.002335 0.735033 0.116046 O 1.453393 2.550967 1.165091 O 2.989216 3.713449 0.085036 N 4.052802 1.205703 0.475334 N 2.362554 1.968159 1.636427 C 2.746354 0.994057 0.754848 C 4.666974 2.312677 1.209557 C 4.680292 0.523200 0.653458 C 4.554565 1.405178 1.925521 C 5.1060 13 0.654048 3.150289 C 6.588329 0.303917 2.905324 C 6.710201 0.579046 1.645636 C 6.172805 0.191654 0.415852 C 5.897847 1.873355 1.859050 C 4.402717 1.524870 2.091454 C 3.912524 0.790636 0.83 6053 C 4.282615 0.633999 3.344840 C 1.030161 2.392556 1.961269 C 0.273538 3.079734 0.986367 C 1.014090 3.515107 1.316643 C 0.856265 3.428513 0.366522 C 3.465455 2.900922 1.968008 C 0.550928 2.273247 3.281658 C 1.554868 3.322003 2.593619 C 0.747357 2.718238 3.561919 C 1.418907 1.775524 4.417456 C 2.955114 3.787684 2.920848 H 4.107724 1.433877 0.052267 H 5.440010 1.934324 1.886283 H 5.128457 3.035067 0.526807 H 3.496995 1.659025 2.077725 H 5.099151 2.348660 1.777912 H 5.017506 1.293489 4.038610 H 7.178425 1.223563 2.784954 H 6.997823 0.226992 3.775073 H 7.764408 0.82 9457 1.471119 H 6.274339 0.408390 0.496836 H 6.756233 1.112968 0.272787 H 5.992476 2.538384 0.991670 H 6.289978 2.420246 2.727794 H 3.837517 2.445867 2.239260 H 3.229231 0.385594 3.533813 H 4.643320 1.184610 4.224004 H 1.599743 4.055343 0.576761 H 0.115593 3.955674 0.975064 H 1.724057 4.092727 0.262397 H 1.195433 2.550301 0.923583 H 3.208413 3.914557 1.638165 H 3.629526 2.928368 3.048963 H 1.125846 2.608208 4.576818 H 2.249335 1.154326 4.076993 H 1.844825 2.627981 4.964704

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225 H 0.829708 1.203281 5.142680 H 3.397251 4.333717 2.082940 H 3.608346 2.936848 3.154510 H 2.95 9003 4.442823 3.800667 N 2.071972 3.689082 0.933644 O 1.711090 4.670957 1.573774 C 4.803597 2.019798 2.352576 H 5.246914 1.445071 3.166668 C 5.685558 3.108279 1.799807 H 6.547651 2.675277 1.278896 H 6.087493 3.734233 2.605854 O 5.029867 3.909567 0.806606 C 4.229712 4.955554 1.143123 O 3.559650 5.467107 0.273552 C 4.236595 5.445967 2.577344 H 5.230405 5.806001 2.866844 H 3.9510 53 4.648151 3.270528 H 3.525342 6.268464 2.654065 C 1.368307 1.183818 3.018890 C 2.694553 0.630962 2.439572 C 0.721880 0.700422 1.609390 C 0.406401 0.009514 2.957146 H 1.505071 1.589555 4.02 7247 H 0.621735 0.703499 3.778895 C 2.244487 0.429347 1.377565 H 2.421066 0.067790 0.358402 C 3.585439 1.712122 1.898342 C 0.111658 0.151461 0.449999 H 3.218721 0.074737 3.226555 H 0.566694 1.776575 1.682092 H 3.172008 2.288770 1.069574 H 0.089646 0.905991 0.276025 H 0.646473 0.278384 3.043529 H 1.001747 2.005461 2.389336 O 2.936061 1.676590 1.551779 C 4.098321 1.954774 0.900640 C 4.824870 1.053650 0.109118 C 4.566718 3.270994 1.057899 C 5.997185 1.476217 0.517597 H 4.503852 0.026495 0.007978 C 5.738030 3.677760 0.435831 H 3.986129 3.955939 1.667340 C 6.462211 2.78 2354 0.362181 H 6.551846 0.777632 1.136148 H 6.087407 4.697859 0.557403 C 7.758490 3.199728 0.989758 F 8.822174 2.932186 0.190594 F 7.794142 4.527009 1.246721 F 7.986301 2.553702 2.157739 C 0.072629 0.954159 0.934154 C 1.222113 1.638485 1.492490 H 0.801356 1.743527 0.729596 H 0.451196 0.246058 1.674293 H 1.219343 2.711048 1.297797 C 1.599273 1.333776 2.934979 H 1.050162 0.468130 3.301206 H 1.354765 2.184707 3.582245 O 2.982039 0.966848 3.116102 C 4.007473 1.866803 3.123556 O 5.135466 1.428519 3.083637 C 3.682365 3.342371 3.192174 H 2.976709 3.572072 3.997519 H 3.251978 3.681876 2.243198 H 4.614358 3.881654 3.365149 TS28* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8325089700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8663780000 a.u Ru 1.069893 0.682450 0.087931 O 0.678051 1.960073 2.336740 O 0.822602 1.463888 0.846286 N 3.460374 1.365297 1.414541 N 3.814329 0.724153 0.879433 C 2.936998 0.317382 0.730287 C 4.666170 1.044955 2.183585 C 2.698152 2.601385 1.596195 C 2.044020 2.646221 2.998917 C 1.175539 3.911424 3.136048 C 2.057462 5.161494 2.945878 C 2.705079 5.121380 1.546656 C 3.589806 3.858831 1.432290 C 1.594924 5.094261 0.474220 C 0.71 7802 3.826179 0.656006 C 1.639741 2.604054 0.480498 C 0.075440 3.875864 2.057117 C 3.885467 1.954272 0.141143 C 3.346058 3.128199 0.703954 C 3.445893 4.322838 0.016304 C 2.736759 3.135508 2.086260 C 5.026039 0.341792 1.639856 C 4.604194 1.997550 1.072266 C 4.097999 4.388623 1.252539 C 4.682493 3.220537 1.750053 C 5.311530 0.788559 1.638840 C 4.163020 5.684303 2.027068 H 2.1864 68 2.745382 0.472177 H 5.454900 1.783518 2.015176 H 4.443503 1.023693 3.258263 H 1.432935 1.747948 3.140004 H 2.822222 2.638998 3.775219 H 0.718649 3.929206 4.134533 H 2.833598 5.200965 3.72 3595 H 1.450927 6.070645 3.053772 H 3.334647 6.009309 1.404747 H 4.093104 3.824304 0.457309 H 4.370855 3.890169 2.205963 H 2.034369 5.105686 0.531816 H 0.973202 5.996190 0.562041

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22 6 H 0.068098 3.823732 0.104837 H 0.573610 3.008337 2.212525 H 0.559573 4.768477 2.139278 H 3.018661 5.228794 0.408958 H 3.519819 3.149917 2.857170 H 2.124819 2.250742 2.272660 H 2.118173 4.024937 2.239354 H 5.229110 1.074800 2.426165 H 5.893558 0.309418 0.971866 H 5.220624 3.255889 2.694906 H 6.332500 0.716202 1.238053 H 5.392347 0.852416 2.725563 H 4.791237 0.144579 1.418569 H 3.252724 5.83 5751 2.622132 H 5.010996 5.694625 2.719354 H 4.258361 6.546984 1.358785 N 0.536491 2.019203 1.982642 O 1.412705 2.549558 2.651906 C 1.427713 4.438392 1.696724 H 0.696025 5.110836 1.249967 C 2.707542 5.123431 2.094364 H 3.524479 4.420330 2.279069 H 2.558402 5.702913 3.012538 O 3.088031 6.118858 1.126883 C 3.756917 5.801844 0.021566 O 3.944701 6.677080 0.830325 C 1.252116 1.408523 3.737546 C 1.929761 2.056131 2.481691 C 1.154099 0.242665 1.931487 C 1.230721 0.114799 3.476191 H 1.788678 1.661682 4.656938 H 2.161805 0.573979 3.823259 C 2.176661 0.860606 1.511974 H 2.11 7489 1.131297 0.454090 C 1.100420 3.150035 1.866119 C 0.279066 0.023923 1.447404 H 2.915767 2.441413 2.749046 H 1.520294 1.203852 1.562788 H 0.103766 2.848334 1.545853 H 0.849487 0.585979 2.165060 H 0.402864 0.616047 3.988286 H 0.233204 1.795794 3.854820 O 3.516079 0.438925 1.824823 C 4.313046 0.207543 0.919022 C 3.860501 0.815352 0.255518 C 5.676536 0.249233 1.251098 C 4.7750 71 1.455033 1.093307 H 2.809531 0.845999 0.510098 C 6.578390 0.885663 0.408773 H 6.004867 0.221760 2.172291 C 6.132888 1.492002 0.772753 H 4.407322 1.945838 1.988826 H 7.631075 0.918913 0.67 0078 C 7.115133 2.129813 1.710448 F 7.573740 1.253246 2.639247 F 8.204207 2.602316 1.058651 F 6.571134 3.162835 2.391422 C 4.249584 4.378478 0.199330 H 4.989617 4.116864 0.565986 H 3.429804 3.656708 0.128969 H 4.718169 4.305141 1.180871 C 0.091475 1.290644 1.430152 C 1.316205 1.221242 2.005081 H 0.089456 1.956092 0.594604 H 0.782092 0.831013 1.882698 H 2.137817 1.798190 1.599876 C 1.553646 0.616849 3.360986 H 1.598910 1.432596 4.098722 H 0.747910 0.063449 3.634104 O 2.822197 0.051931 3.345776 C 3.163476 0.998538 4.269025 O 4.271646 1.476285 4.200409 C 2.132234 1.39 8250 5.301540 H 1.727454 0.531784 5.835922 H 1.301172 1.916192 4.810483 H 2.610160 2.072118 6.013050 TS29* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8286104100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 29 07.8657387400 a.u Ru 1.503854 0.742888 0.274759 O 1.498878 2.160946 2.270346 O 0.206064 1.941234 0.945973 N 4.089582 0.761352 1.055485 N 3.891882 1.294937 0.330452 C 3.279226 0.067872 0.351581 C 5.215710 0.085610 1.704215 C 3.624585 2.104418 1.410292 C 3.009941 2.116607 2.829661 C 2.411377 3.504714 3.128627 C 3.535520 4.558876 3.064617 C 4.164840 4.550281 1.655781 C 4.763517 3.152289 1.368409 C 3.074721 4.889446 0.616705 C 1.949036 3.822346 0.667493 C 2.585181 2.459436 0.330736 C 1.327905 3.826723 2.078837 C 3.634324 2.402101 0.547787 C 3.084050 3.584479 0.021083 C 2.8 80515 4.669125 0.883624 C 2.740703 3.719298 1.445199 C 5.221116 1.267205 0.984040 C 4.040577 2.331749 1.898566 C 3.227928 4.615997 2.235271 C 3.821100 3.442534 2.716774 C 4.682153 1.086505 2 .469776 C 2.955360 5.778128 3.160034 H 3.150783 2.586296 0.605732

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227 H 6.147842 0.641704 1.571988 H 5.032256 0.022168 2.781785 H 2.241030 1.339777 2.887649 H 3.779633 1.872855 3.576356 H 1.967826 3.499663 4.133536 H 4.299577 4.345078 3.825660 H 3.131915 5.555444 3.287982 H 4.968885 5.296045 1.606128 H 5.242515 3.134288 0.380611 H 5.539003 2.926020 2.115501 H 3.506472 4.928047 0.3920 45 H 2.663191 5.886768 0.826700 H 1.181025 4.079153 0.069169 H 0.514704 3.094285 2.136917 H 0.886687 4.810607 2.289389 H 2.438210 5.579394 0.484428 H 3.627617 3.977906 2.039903 H 2.338894 2.791146 1.861841 H 2.007801 4.516764 1.602699 H 5.335002 2.117116 1.662572 H 6.011726 1.330233 0.225778 H 4.115745 3.387703 3.762467 H 5.593689 0.807703 1.927629 H 4.956434 1.243387 3.516861 H 4.010563 0.221334 2.424251 H 2.056411 5.593264 3.761837 H 3.784819 5.938289 3.857793 H 2.794882 6.706343 2.602613 N 0.305800 2.509307 1.994511 O 0.335956 3.304151 2.660401 C 2.086320 4.054 718 2.688828 H 1.667776 4.982535 2.300781 C 3.268400 4.260729 3.597352 H 3.853059 3.347789 3.744064 H 2.931605 4.595557 4.585129 O 4.100951 5.341399 3.142110 C 5.040154 5.176547 2.162526 O 5.641337 6.150468 1.782384 C 0.843098 0.882690 3.802707 C 1.884103 1.512982 2.820930 C 0.758284 0.446783 1.741446 C 0.603999 0.548712 3.288064 H 1.204201 0.898678 4.835673 H 1.384380 1.221655 3.659001 C 2.014249 0.479778 1.658550 H 2.159358 0.953089 0.683245 C 1.500998 2.894921 2.362860 C 0.545044 0.082268 1.147157 H 2.864627 1.543109 3.301580 H 0.994741 1.413595 1.291916 H 0.620 753 2.948337 1.721314 H 0.946290 0.923052 1.726531 H 0.359095 0.957235 3.602551 H 0.088046 1.461340 3.789000 O 3.198552 0.267580 1.981058 C 3.872390 0.989845 1.033938 C 3.373229 1.327350 0.2 28425 C 5.154076 1.416054 1.417037 C 4.160375 2.085283 1.097272 H 2.368275 1.064820 0.530567 C 5.930168 2.163977 0.543259 H 5.518011 1.149549 2.404198 C 5.437627 2.502650 0.723676 H 3.754348 2.373049 2.061475 H 6.918678 2.494385 0.845240 C 6.302703 3.265308 1.684314 F 7.096615 2.441789 2.413321 F 7.128680 4.125635 1.043581 F 5.573602 3.982566 2.566795 C 5.290545 3.777693 1.632488 H 5.686307 3.122980 2.417873 H 4.372826 3.320858 1.249236 H 6.025933 3.849548 0.831020 C 0.351330 1.298178 0.683194 C 0.994679 0.772036 1.826002 H 0.806735 2.137947 0.172769 H 0.732833 1.2 62577 0.657672 H 1.931699 1.234993 2.108848 C 0.169168 0.343270 3.016307 H 0.761645 0.140636 2.705222 H 0.733450 0.337327 3.656208 O 0.135804 1.562553 3.734803 C 0.731878 1.539004 4.961440 O 0.940887 2.590230 5.517813 C 1.092524 0.189570 5.552056 H 1.724756 0.395617 4.875775 H 0.194995 0.406686 5.752582 H 1.623205 0.360519 6.488876 TS30E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8152030 600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8570331700 a.u Ru 1.652036 0.670582 0.218980 O 0.775180 3.056298 2.358147 O 0.147541 1.695179 0.885746 N 4.208686 0.761379 1.132391 N 3.989669 1.346657 0.582706 C 3.366532 0.129396 0.556284 C 5.365629 0.141043 1.783167 C 3.706028 2.114980 1.391827 C 2.924010 2.141383 2.732699 C 2.300350 3.530152 2.960560 C 3.425381 4.585085 2.999549 C 4.200422 4.561974 1.665828 C 4.834416 3.165314 1.461832 C 3.222660 4.874289 0.513590 C 2.099959 3.805194 0.461082 C 2.766131 2.435811 0.202048

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228 C 1.332344 3.830629 1.798594 C 3.469574 2.631 628 0.205399 C 2.808464 3.399839 1.191249 C 2.287963 4.646066 0.835822 C 2.722585 2.934412 2.628259 C 5.356489 1.256281 1.145885 C 3.711285 3.168515 1.073552 C 2.435306 5.167998 0.456027 C 3.166925 4.423666 1.382064 C 4.580858 2.492131 2.111450 C 1.828374 6.499511 0.831010 H 3.399587 2.545128 0.687888 H 6.285876 0.692454 1.575251 H 5.227934 0.101537 2.873242 H 2.137008 1.373694 2.703746 H 3.596308 1.882568 3.563984 H 1.756988 3.533239 3.914832 H 4.104130 4.383293 3.840501 H 2.998549 5.582846 3.166293 H 5.000289 5.313325 1.691384 H 5.419890 3.141018 0.533023 H 5.523689 2.950300 2.292451 H 3.757106 4.900453 0.445347 H 2.785944 5.871966 0.661902 H 1.428715 4.049246 0.363386 H 0.515653 3.095510 1.785142 H 0.865523 4.814136 1.943513 H 1.769398 5.233390 1.590740 H 3.698137 3.015283 3.126697 H 2.407622 1.890895 2.718315 H 2.022304 3.554314 3.195679 H 5.533091 2.060128 1.865221 H 6.098992 1.348368 0.342626 H 3.336901 4.830311 2.376929 H 5.434 624 3.135580 2.358032 H 4.030456 2.317716 3.042777 H 4.976460 1.533919 1.766849 H 0.813509 6.371941 1.230119 H 2.417497 7.004951 1.603072 H 1.756172 7.166179 0.034742 N 0.239169 2.692231 1.7 42459 O 1.351116 3.198816 1.896546 C 2.897363 4.495041 1.243050 H 2.600077 5.354562 0.643270 C 4.240406 4.660014 1.903213 H 4.662196 3.711875 2.248333 H 4.157173 5.319666 2.774509 O 5.165865 5.353525 1.046487 C 5.852145 4.719616 0.048716 O 6.545465 5.388499 0.677322 C 1.099601 1.968339 3.191210 C 2.243204 2.195586 2.145836 C 0.834569 0.272716 1.456788 C 0.586714 0.529165 2.957970 H 1.453995 2.120709 4.215063 H 1.178371 0.182561 3.541874 C 2.251609 0.896917 1.276836 H 2.510467 1.075277 0.228009 C 2.055285 3.458389 1.345199 C 0.212067 0.988794 0.592773 H 3.208013 2.2 19085 2.656101 H 0.881229 0.792599 1.212711 H 1.106847 3.534173 0.812837 H 0.840419 1.693194 1.126450 H 0.462720 0.403872 3.246849 H 0.295941 2.695218 3.027258 O 3.255185 0.071621 1.884053 C 3.955207 0.856174 1.155079 C 3.480238 1.485454 0.001159 C 5.220275 1.183064 1.667748 C 4.283146 2.429830 0.641660 H 2.483696 1.304611 0.382788 C 6.010940 2.122277 1.020200 H 5.560227 0.689203 2.572615 C 5.547334 2.747268 0.144700 H 3.890934 2.934691 1.516809 H 6.987930 2.375755 1.419394 C 6.433519 3.716244 0.871512 F 7.296340 3.083652 1.706402 F 7.194716 4.441347 0.016243 F 5.7 30523 4.587276 1.626198 C 5.721366 3.213528 0.072283 H 6.112476 2.707033 0.817765 H 4.676554 2.911182 0.193866 H 6.298619 2.894502 0.940217 C 0.139130 1.162350 0.776368 C 2.179160 0.072926 1 .881655 H 0.683880 1.971385 1.251832 H 0.617724 0.664025 1.372681 H 3.014390 0.620106 1.991492 C 1.614183 0.426530 3.227298 H 0.535507 0.594211 3.209418 H 2.087362 1.357204 3.566709 O 1.943491 0.671134 4.106667 C 1.706963 0.616684 5.451460 O 2.034159 1.563090 6.125206 C 1.048734 0.631157 6.003220 H 0.080171 0.819247 5.527275 H 1.669068 1.517983 5.831745 H 0.905687 0.494777 7.075275 TS31* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8200033300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8571992800 a.u Ru 1.920143 0.123729 0.547367 O 0.522479 0.585250 3.136510 O 1.039596 0.797056 2.415243 N 4.279217 0.651216 1.042311

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229 N 3.042615 0.608740 2.340324 C 3.099052 0.017387 1.106230 C 4.989097 0.712447 2.322339 C 4.544617 1.521280 0.108619 C 4.046914 2.962647 0.174805 C 4.2105 66 3.836920 1.082588 C 5.702060 3.878852 1.472620 C 6.200051 2.446180 1.755506 C 6.043513 1.585772 0.476937 C 5.371682 1.847433 2.914097 C 3.873331 1.790313 2.518114 C 3.756065 0.887310 1.27 4663 C 3.380543 3.222471 2.227555 C 2.124646 1.616075 2.795120 C 1.084467 1.250210 3.673555 C 0.189582 2.237859 4.099705 C 0.949885 0.153702 4.221972 C 4.286035 0.398516 3.113956 C 2.330658 2.970333 2.451078 C 0.317565 3.573698 3.707819 C 1.405476 3.919218 2.899587 C 3.542503 3.447361 1.676137 C 0.685156 4.616519 4.142586 H 4.262771 0.063105 1.513165 H 6.059642 0.531551 2.196618 H 4.860142 1.697695 2.791762 H 2.992390 2.926668 0.476254 H 4.610513 3.395466 1.014331 H 3.856145 4.853323 0.865117 H 6.293113 4.336163 0.666160 H 5.840324 4.505117 2.363924 H 7.261555 2.47 3199 2.033939 H 6.425931 0.570315 0.646437 H 6.636141 2.029535 0.337335 H 5.736104 0.840472 3.160218 H 5.503852 2.463660 3.814703 H 3.286808 1.365545 3.338511 H 2.315899 3.204313 1.965333 H 3.475367 3.840299 3.130950 H 0.625012 1.954403 4.763208 H 1.439888 0.231267 5.202270 H 1.407679 0.901821 3.570594 H 0.101786 0.420177 4.372014 H 4.055747 0.116005 4.145062 H 4.874420 1.325052 3.135846 H 1.545997 4.959222 2.612318 H 4.264269 3.916525 2.358104 H 3.264499 4.202906 0.933824 H 4.057239 2.637757 1.154166 H 1.404435 4.829005 3.341115 H 0.194611 5.563486 4.392519 H 1.254218 4.286129 5.017415 N 0.133805 0.585497 2.957816 O 0.804868 1.569202 3.281326 C 4.583954 4.044021 2.274974 H 5.280762 4.014062 3.111643 C 4.965872 5.038838 1.212522 H 4.428372 4.883685 0.273231 H 4.747840 6.057763 1.553120 O 6.389335 5.044426 1.006706 C 7.006106 4.173849 0.150750 O 8.212499 4.147438 0.143331 C 1.008419 3.541583 1.825693 C 2.399149 3.141768 1.296259 C 0.70 0100 1.667930 0.229518 C 0.036206 2.969277 0.776164 H 0.909179 4.622603 1.965733 H 0.101689 3.685327 0.041331 C 2.166225 1.700846 0.797232 H 2.268350 0.996453 1.633602 C 3.504057 3.253912 2. 307221 C 0.045704 0.403889 0.643246 H 2.618453 3.747018 0.408215 H 0.795163 1.727928 0.855825 H 3.379150 2.614792 3.184300 H 0.322179 0.399326 1.694126 H 0.953351 2.777719 1.203439 H 0.838923 3.073021 2.805772 O 3.147109 1.408755 0.202548 C 3.538840 0.108895 0.423082 C 4.056914 0.696999 0.598791 C 3.481521 0.364452 1.738220 C 4.488114 1.988564 0.305448 H 4.143258 0.308780 1.60887 2 C 3.924293 1.653091 2.024613 H 3.061803 0.270119 2.511422 C 4.420990 2.472154 1.005088 H 4.897186 2.614801 1.091540 H 3.874892 2.023552 3.043155 C 4.816487 3.888785 1.307453 F 5.746867 4. 353384 0.443951 F 5.314132 4.022325 2.555622 F 3.755663 4.736081 1.221330 C 6.142355 3.331476 0.766223 H 5.596536 3.966213 1.475013 H 5.402463 2.737718 0.221463 H 6.800870 2.668500 1.327967 C 0.171031 0.863170 0.069619 C 1.837758 1.720145 0.763134 H 0.112596 1.740649 0.705658 H 0.756745 0.965128 0.837881 H 1.962032 2.423109 0.060664 C 1.772041 2.431413 2.092112 H 0.940471 2.075074 2.704186 H 2.697984 2.222186 2.643698 O 1.772111 3.855679 1.881565 C 0.633045 4.613810 1.910744 O 0.706967 5.753251 1.517668

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230 C 0.632118 3.995942 2.467925 H 0.928013 3.092647 1.927844 H 0.496509 3.708928 3.516847 H 1.432296 4.731222 2.390635 TS32* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8308460300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8607298900 a.u Ru 1.935206 0.209518 0.118253 O 1.834808 0.050075 2.386821 O 0.957897 1.690754 1.438647 N 4.499994 0.955730 0.554237 N 3.043126 2.280918 1.508073 C 3.166579 1.158819 0.729967 C 5.334645 2.055386 1.046303 C 4.965115 0.0 39635 0.418375 C 5.201472 0.616579 1.803383 C 5.631795 0.452322 2.829400 C 6.920641 1.147957 2.350271 C 6.658842 1.814803 0.984872 C 6.278968 0.718740 0.038043 C 5.513746 2.843090 1.130042 C 4.212519 2.128584 1.591436 C 3.854761 1.106076 0.483251 C 4.500472 1.487775 2.968337 C 1.867932 3.008497 1.882927 C 1.359937 3.976951 0.990010 C 0.254621 4.735281 1.384964 C 2.012256 4.221486 0.352260 C 4.352053 2.809562 1.947847 C 1.317652 2.856009 3.169409 C 0.343736 4.574674 2.641320 C 0.208809 3.638563 3.518240 C 1.905023 1.906819 4.189674 C 1.556542 5.386782 3.032620 H 3.9 32162 1.666833 0.457875 H 6.205684 1.682404 1.591137 H 5.691623 2.676700 0.213330 H 4.278140 1.104441 2.136022 H 5.979024 1.390146 1.722988 H 5.811385 0.032885 3.797862 H 7.742294 0.421929 2 .266283 H 7.234550 1.902041 3.084516 H 7.568873 2.322919 0.639334 H 6.137395 1.150965 1.037971 H 7.100684 0.009760 0.109270 H 5.345765 3.359528 0.174729 H 5.803265 3.611502 1.860779 H 3.410028 2.869467 1.688038 H 3.613176 1.007557 3.383047 H 4.801042 2.273309 3.675807 H 0.140995 5.482084 0.699657 H 3.040234 4.588184 0.235992 H 2.069226 3.310894 0.958280 H 1.457350 4.974319 0.919992 H 4.392093 3.894883 1.818854 H 4.510608 2.586179 3.011076 H 0.226766 3.514752 4.507742 H 2.551542 2.444472 4.896252 H 1.117479 1.426275 4.779581 H 2.507826 1.123899 3.723834 H 2.4843 44 4.893309 2.713561 H 1.617578 5.518714 4.117725 H 1.541271 6.378876 2.569108 N 1.219048 1.067594 2.538699 O 0.905764 1.505180 3.629933 C 4.861788 3.874288 0.926589 H 5.199804 4.589045 0.17 7296 C 5.841664 3.675464 2.050345 H 5.606474 2.805229 2.668903 H 5.850598 4.553607 2.706059 O 7.190643 3.611652 1.550445 C 7.741654 2.450536 1.086860 O 8.826795 2.506786 0.561771 C 1.665267 2.853848 2.322097 C 2.974009 2.322452 1.687933 C 1.073889 0.693206 1.382389 C 0.865974 1.580172 2.632439 H 1.860217 3.473920 3.203291 H 1.292353 1.079369 3.509750 C 2.560414 1.001597 0.971397 H 2.667680 1.090294 0.113381 C 3.658368 3.305950 0.779861 C 0.097811 1.034991 0.260232 H 3.643110 2.019431 2.499438 H 1.013001 0.372615 1.614189 H 3.071392 3.597525 0.093951 H 0.295804 2.04 5751 0.277653 H 0.189297 1.763890 2.843327 H 1.125680 3.482591 1.600498 O 3.462062 0.006721 1.466156 C 3.560946 1.222769 0.843412 C 3.460447 1.415532 0.541654 C 3.850684 2.312676 1.676232 C 3.639404 2.689567 1.080638 H 3.266604 0.583525 1.209056 C 4.035118 3.578507 1.133438 H 3.926175 2.143358 2.745303 C 3.926483 3.774521 0.247909 H 3.553326 2.834449 2.152778 H 4.261789 4.417170 1.783319 C 4.056952 5.151728 0.829538 F 4.819733 5.959018 0.058772 F 2.846751 5.766550 0.946537 F 4.598080 5.134733 2.064662 C 6.981230 1.156050 1.298751 H 6.894980 0.927203 2.367800 H 5.967544 1.194240 0.890013

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231 H 7.541469 0.356279 0.813795 C 0.160767 0.416468 0.989488 C 1.519202 0.982394 1.544160 H 0.097161 0.976965 1.878905 H 0.844356 0.415030 1.140776 H 1.690281 0.559614 2.542324 C 0.943521 2.365879 1.652364 H 0.512300 2.712337 0.709156 H 1.777413 3.036287 1.919757 O 0.053420 2.371272 2.697067 C 0.709337 3.511990 3.062355 O 1.621532 3.415380 3.849157 C 0.244 151 4.821435 2.462189 H 0.372962 4.824410 1.375046 H 0.815100 5.002634 2.676097 H 0.847207 5.623257 2.886501 TS33* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8168359200 a.u. M06/SDD/6 311++G(d,p) SCF energy in so lution: 2907.8570887400 a.u Ru 1.427475 0.975716 0.203769 O 1.454414 0.992780 2.210705 O 0.180402 2.267364 0.925727 N 3.921045 1.269425 1.248209 N 3.947912 0.825526 0.613158 C 3.207755 0.324224 0. 578127 C 5.111323 0.743041 1.923581 C 3.282417 2.538372 1.608542 C 2.691538 2.460261 3.041544 C 1.922190 3.754339 3.367279 C 2.891400 4.951166 3.280589 C 3.482521 5.034037 1.857579 C 4.262453 3.734256 1.546462 C 2.331486 5.217577 0.845620 C 1.361217 4.010417 0.921195 C 2.155996 2.738466 0.586821 C 0.779326 3.925639 2.347199 C 3.700735 2.093965 0.015102 C 3.083106 3.117653 0.73469 4 C 2.861868 4.355312 0.121506 C 2.736588 2.946970 2.196960 C 5.264382 0.629287 1.258736 C 4.191104 2.351487 1.311931 C 3.269903 4.616570 1.191144 C 3.948554 3.607770 1.879334 C 5.003535 1. 344202 2.099154 C 2.983707 5.947329 1.845874 H 2.639319 2.894233 0.417026 H 5.979613 1.388807 1.768300 H 4.935847 0.659129 3.004370 H 2.025690 1.590996 3.102893 H 3.499097 2.311729 3.772187 H 1.512312 3.683668 4.383632 H 3.695650 4.841421 4.021978 H 2.362048 5.882877 3.519843 H 4.173739 5.884451 1.794334 H 4.716558 3.786190 0.547674 H 5.079907 3.611580 2.272275 H 2.731503 5.315213 0.173059 H 1.790433 6.148661 1.064535 H 0.552826 4.135237 0.198327 H 0.077862 3.084321 2.414938 H 0.209198 4.837497 2.570676 H 2.374704 5.142570 0.693538 H 3.572978 3.274579 2.830018 H 2.522592 1.908330 2.458328 H 1.871249 3.559159 2.468733 H 5.467665 1.434533 1.970146 H 6.056449 0.637180 0.499186 H 4.302818 3.798790 2.890060 H 6.062435 1.634359 2.110354 H 4.670072 1.30 0686 3.141479 H 4.940963 0.335325 1.683821 H 2.035828 5.917511 2.398919 H 3.766829 6.217627 2.561710 H 2.904813 6.750597 1.105983 N 1.195201 2.125531 1.736586 O 1.859571 3.123420 1.998432 C 1.327968 4.654491 1.572023 H 0.709391 5.377258 1.041048 C 2.399708 5.285523 2.419210 H 3.181564 4.576193 2.706296 H 1.967621 5.687012 3.342951 O 2.959325 6.444573 1.777039 C 3.934112 6.349860 0.822861 O 4.282229 7.360806 0.264818 C 0.931815 1.521682 3.251041 C 1.759595 2.195479 2.100627 C 1.012417 0.072000 1.373822 C 0.894514 0.011215 2.928377 H 1.382740 1.717548 4.228643 H 1.76 2696 0.496139 3.359450 C 2.097624 1.026414 1.130774 H 2.186641 1.336293 0.084456 C 1.054398 3.349416 1.437560 C 0.368966 0.200203 0.812341 H 2.717004 2.538910 2.498861 H 1.380161 1.043051 1. 035378 H 0.214357 3.090509 0.793950 H 0.814109 1.111873 1.220055 H 0.003436 0.481830 3.312322 H 0.079952 1.938509 3.285073 O 3.364996 0.561259 1.622899 C 4.186761 0.273704 0.913362 C 3.954633 0.710689 0.390570 C 5.345725 0.678113 1.596628 C 4.875562 1.562760 1.004626 H 3.065125 0.428521 0.938100

PAGE 239

232 C 6.260429 1.514124 0.973724 H 5.504553 0.326376 2.611145 C 6.028785 1.965248 0.33345 0 H 4.664368 1.926554 2.003784 H 7.152959 1.830350 1.504845 C 7.048544 2.840768 0.999973 F 8.125741 2.130376 1.421555 F 7.527636 3.785363 0.153713 F 6.552970 3.478754 2.080729 C 4.538793 4.987383 0.543869 H 5.058078 4.597141 1.427095 H 3.774852 4.257934 0.256984 H 5.259232 5.099587 0.266498 C 0.711788 0.979468 1.425123 C 1.683300 0.184485 2.057575 H 1.022055 1.907699 0.958601 H 0.329462 0.873479 1.703295 H 2.696795 0.560326 2.049713 C 1.397602 0.639596 3.297022 H 0.329231 0.814045 3.409021 H 1.927361 1.600635 3.274026 O 1.924438 0.143883 4.394203 C 1.640042 0.161 555 5.693102 O 2.166969 0.490494 6.562295 C 0.667882 1.293452 5.960830 H 0.326363 1.063377 5.561319 H 0.996104 2.229460 5.495536 H 0.597519 1.431004 7.040036 18* B3LYP/SDD/6 31G(d) SCF energy in gas p ha se: 2908.8369466300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8722885700 a.u Ru 1.063823 0.639229 0.263303 O 0.400120 2.538841 2.317230 O 0.764733 1.766725 0.635004 N 3.711969 0.925929 0.910064 N 3.745291 1.148779 0.226633 C 2.963489 0.025848 0.319402 C 5.100975 0.539308 1.171970 C 3.121233 2.191410 1.348308 C 2.743841 2.091638 2.847797 C 2.032747 3.380188 3.299243 C 2.972915 4.583892 3.085849 C 3.347074 4.685703 1.592530 C 4.077474 3.394410 1.153608 C 2.058483 4.877176 0.765044 C 1.120470 3.656878 0.963358 C 1.880568 2.412582 0.470915 C 0.753080 3.550331 2.457345 C 3.388 667 2.494918 0.125330 C 2.780019 3.336297 0.827994 C 2.457795 4.648870 0.457557 C 2.563733 2.920618 2.265763 C 5.082056 0.957966 0.835659 C 3.793371 3.014556 1.375870 C 2.766112 5.162068 0.8 04025 C 3.456144 4.332934 1.695096 C 4.620640 2.203731 2.347183 C 2.375036 6.567960 1.194295 H 2.251881 2.633321 0.549869 H 5.777346 1.104825 0.521927 H 5.378185 0.734439 2.212965 H 2.088632 1.224762 2.993608 H 3.650167 1.924530 3.447747 H 1.772654 3.297353 4.362987 H 3.878041 4.469868 3.699366 H 2.479979 5.509339 3.412629 H 4.017660 5.540483 1.436431 H 4.380441 3.453838 0.101154 H 4.989905 3.268430 1.754924 H 2.300887 4.993676 0.299158 H 1.548318 5.797969 1.080456 H 0.209519 3.805621 0.378544 H 0.077692 2.702326 2.622868 H 0.213737 4.455124 2.769189 H 1.973109 5.2 91809 1.189683 H 3.335221 3.369471 2.906001 H 2.609410 1.839578 2.405854 H 1.597986 3.276431 2.638216 H 5.178650 1.593471 1.724879 H 5.867778 1.241716 0.129854 H 3.750128 4.725363 2.666474 H 5.691466 2.319676 2.128792 H 4.469540 2.554693 3.373489 H 4.393893 1.136935 2.302700 H 1.424094 6.575962 1.743067 H 3.127031 7.026911 1.845127 H 2.248952 7.208506 0.315426 N 0.683725 2.539830 1.680561 O 1.656069 3.218293 1.995082 C 1.502371 4.460937 1.021880 H 0.795221 5.065445 0.455074 C 2.718756 5.221464 1.476758 H 3.548803 4.564646 1.752722 H 2.481379 5.835195 2.353280 O 3.1 27627 6.188167 0.491515 C 3.880494 5.846327 0.595796 O 4.087646 6.690628 1.432570 C 1.282405 1.735747 3.386188 C 1.996077 2.177415 2.058981 C 1.111043 0.121024 1.786972 C 1.120433 0.198226 3 .304371 H 1.859827 2.038019 4.265093 H 1.979162 0.300014 3.764928 C 2.226505 0.847736 1.285986 H 2.242800 0.968200 0.198451 C 1.197236 3.179481 1.268485 C 0.269376 0.151955 1.199062

PAGE 240

233 H 2.983982 2.585023 2.285296 H 1.413144 1.147875 1.568229 H 0.246087 2.818777 0.877216 H 0.823141 0.890583 1.788951 H 0.218720 0.156164 3.815491 H 0.306865 2.226330 3.470180 O 3.516639 0.405261 1.7400 71 C 4.314854 0.412152 0.986175 C 3.874557 1.192494 0.086690 C 5.663317 0.447496 1.375643 C 4.789192 1.995787 0.769712 H 2.830515 1.228705 0.370333 C 6.564795 1.248056 0.687767 H 5.979878 0.160040 2.217654 C 6.132835 2.026283 0.394197 H 4.429742 2.617527 1.582770 H 7.605988 1.275412 0.992793 C 7.122461 2.843251 1.170928 F 7.700136 2.127451 2.169227 F 8.134168 3.290003 0.387952 F 6.552302 3.922652 1.750073 C 4.436147 4.437238 0.672862 H 5.132644 4.241895 0.150914 H 3.640942 3.686847 0.620774 H 4.971597 4.338251 1.617263 C 0.006869 0.617803 1.973896 C 1.361664 0.694 157 2.200120 H 0.508866 1.416750 1.451588 H 0.619169 0.085509 2.510921 H 1.905322 1.573875 1.885141 C 2.018714 0.169902 3.253075 H 2.372095 0.463897 4.077744 H 1.306434 0.900345 3.634085 O 3.162883 0.836763 2.672664 C 3.669965 2.001662 3.172983 O 4.604944 2.501662 2.590042 C 3.025231 2.597733 4.404309 H 2.927749 1.865397 5.212721 H 2.023506 2.968227 4.158574 H 3.643854 3.430862 4.739316 19* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8452815400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8897986400 a.u Ru 1.725449 0.678234 0.198915 O 1.372159 3.098748 2.002375 O 0.126588 2.095488 0.491502 N 4.421670 0.066724 0.695359 N 3.655963 1.878813 0.055009 C 3.329992 0.558342 0.177957 C 5.474082 0.854397 1.134517 C 4.259912 1.429466 1.202027 C 3.801643 1.405235 2.685482 C 3.5152 37 2.835882 3.177977 C 4.799953 3.679788 3.047961 C 5.251323 3.707860 1.572713 C 5.553653 2.267538 1.096275 C 4.128021 4.323474 0.712652 C 2.836032 3.471297 0.835189 C 3.169691 2.060454 0.32 1042 C 2.393677 3.443497 2.312407 C 2.901447 2.949817 0.535065 C 2.174743 3.815495 0.306542 C 1.448522 4.860360 0.277534 C 2.219210 3.695186 1.813354 C 5.068668 2.141602 0.408664 C 2.988306 3.198086 1.921097 C 1.453848 5.086507 1.657429 C 2.245243 4.254776 2.456291 C 3.887543 2.392035 2.834113 C 0.629408 6.192349 2.272779 H 3.544621 2.134231 0.718284 H 6.466297 0.498607 0.845493 H 5.455316 0.974300 2.226644 H 2.899435 0.784188 2.767745 H 4.577943 0.939529 3.308898 H 3.200145 2.800185 4.229053 H 5.594162 3.260263 3.681737 H 4.616077 4.702613 3.402202 H 6.163636 4.31 0462 1.477278 H 5.907104 2.270813 0.056717 H 6.352383 1.832622 1.715062 H 4.437500 4.382950 0.338975 H 3.926426 5.351103 1.045195 H 2.057641 3.917918 0.214839 H 1.469829 2.860453 2.421785 H 2.167121 4.463306 2.651008 H 0.873612 5.521651 0.367490 H 3.067128 4.262675 2.221816 H 2.332771 2.661333 2.148038 H 1.311947 4.107899 2.264963 H 5.150784 3.036182 1.031691 H 5.656764 2.303168 0.504056 H 2.285478 4.429311 3.529232 H 4.851461 2.900549 2.971600 H 3.436906 2.282961 3.825607 H 4.095126 1.392423 2.444172 H 0.269059 5.788993 2.757063 H 1.193592 6.731117 3.042067 H 0.30 3137 6.916868 1.520108 N 0.268968 3.008114 1.430865 O 0.705277 3.706151 1.701706 C 2.643998 4.252143 1.715491 H 2.376813 5.121803 1.116077 C 3.805349 4.492681 2.641579 H 4.242080 3.564050 3. 020150 H 3.484668 5.081037 3.508895 O 4.806093 5.323071 2.025179

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234 C 5.743956 4.819908 1.167754 O 6.489030 5.595708 0.621636 C 0.904968 1.559557 3.333762 C 2.083647 1.838468 2.341486 C 0.743455 0.102035 1.545225 C 0.448036 0.114158 3.046942 H 1.215316 1.701680 4.373674 H 1.046255 0.592908 3.631256 C 2.131613 0.588269 1.408875 H 2.398100 0.838164 0.375831 C 1.917943 3.133197 1.59050 0 C 0.365586 0.521037 0.678086 H 3.029635 1.844554 2.887798 H 0.842229 1.161311 1.304639 H 1.085168 3.161493 0.886560 H 0.779364 1.412799 1.148087 H 0.604788 0.054149 3.300017 H 0.087532 2.265963 3.152822 O 3.176500 0.228773 1.966114 C 3.771308 1.228560 1.244321 C 3.228978 1.839537 0.108187 C 5.010811 1.660029 1.744419 C 3.928213 2.873952 0.516555 H 2.249289 1.578666 0.269422 C 5.701393 2.683775 1.111685 H 5.409693 1.177699 2.631181 C 5.163823 3.297225 0.027468 H 3.476025 3.367249 1.369940 H 6.657058 3.015145 1.505239 C 5.940593 4.368018 0.735384 F 6.828314 3.848 901 1.620956 F 6.662042 5.121943 0.129058 F 5.141307 5.204082 1.432534 C 5.812873 3.316900 0.976968 H 6.090229 2.814081 1.910950 H 4.852462 2.906200 0.650668 H 6.574929 3.108367 0.225857 C 0.075908 0.821378 0.858180 C 1.167104 0.292533 1.867475 H 0.064876 1.909108 0.966594 H 0.884893 0.389058 1.140271 H 1.829153 1.088132 2.189924 C 0.635169 0.425128 3.091591 H 0.220848 1.061591 2.858614 H 1.419976 1.038628 3.543770 O 0.233310 0.618647 4.010740 C 0.306349 0.329188 5.230472 O 0.577708 1.245862 5.968314 C 0.535592 1.128777 5.576854 H 1.229122 1.602390 4.873019 H 0.397 057 1.702486 5.543849 H 0.954893 1.176963 6.581988 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8473440800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8893698400 a.u Ru 1.879080 0.253529 0.178671 O 1.561 159 0.326006 2.696136 O 1.004028 1.901255 1.306180 N 4.294077 1.090659 0.690698 N 2.707887 2.129311 1.781296 C 2.944527 1.161918 0.841553 C 5.035574 2.132952 1.405289 C 4.855515 0.310246 0.4 09427 C 5.123295 1.215013 1.642703 C 5.650584 0.368043 2.817477 C 6.950815 0.345649 2.398717 C 6.667339 1.257342 1.187467 C 6.176127 0.391647 0.006900 C 5.585339 2.292779 1.562486 C 4.273277 1.565517 1.973940 C 3.806698 0.752835 0.755459 C 4.579068 0.671015 3.194627 C 1.475434 2.756738 2.169431 C 0.992599 3.822771 1.374841 C 0.167563 4.485800 1.776946 C 1.722499 4.256682 0.123994 C 3.956759 2.698104 2.336897 C 0.849232 2.426388 3.384065 C 0.848902 4.139518 2.952852 C 0.316929 3.120408 3.742190 C 1.393783 1.388268 4.340264 C 2.118200 4.856070 3.350892 H 3.718390 1.4 55243 0.111140 H 5.885078 1.714663 1.952217 H 5.418812 2.889116 0.707010 H 4.190640 1.719263 1.925542 H 5.855503 1.991368 1.380602 H 5.848274 1.026274 3.673472 H 7.728093 0.389096 2.144508 H 7.337424 0.941893 3.235803 H 7.587621 1.776306 0.889600 H 6.004387 1.009755 0.884612 H 6.945381 0.350314 0.252242 H 5.397602 2.969183 0.717219 H 5.936012 2.915243 2.396947 H 3.522135 2.316870 2.236047 H 3.666824 0.176405 3.535957 H 4.939106 1.298979 4.021081 H 0.542932 5.304824 1.167119 H 2.748649 4.576021 0.345497 H 1.793173 3.447529 0.610982 H 1.211154 5.099962 0.349099 H 3.9 14396 3.790987 2.333290 H 4.089345 2.368671 3.375048 H 0.809648 2.859224 4.676667 H 1.583424 1.838785 5.322200 H 0.676251 0.573956 4.494963

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235 H 2.326635 0.945591 3.986198 H 2.990923 4.432786 2 .835883 H 2.304964 4.774138 4.426273 H 2.075540 5.919666 3.092111 N 1.075245 1.483023 2.537270 O 0.678856 2.183304 3.455997 C 4.770470 3.842604 0.899360 H 5.210119 4.477173 0.130756 C 5.623699 3.717149 2.131664 H 5.298907 2.908695 2.791881 H 5.595733 4.647894 2.709923 O 7.012312 3.577338 1.777658 C 7.572379 2.364232 1.491013 O 8.698232 2.347941 1.056250 C 1.414043 3.039892 2.0395 21 C 2.755865 2.421470 1.587797 C 0.883569 0.744208 1.404569 C 0.588982 1.821426 2.478469 H 1.551867 3.785452 2.830013 H 0.935878 1.471379 3.457929 C 2.357444 1.062617 0.948517 H 2.438989 1.104413 0.143423 C 3.567462 3.298734 0.677065 C 0.116149 0.816629 0.249494 H 3.326478 2.166910 2.487523 H 0.894565 0.259587 1.830212 H 3.084156 3.527243 0.275371 H 0.235801 1.846269 0.080556 H 0.479853 2.027284 2.573051 H 0.934396 3.550621 1.193941 O 3.305010 0.096154 1.453524 C 3.336235 1.159788 0.894910 C 3.551441 1.372548 0.471839 C 3.200720 2.251564 1.761382 C 3.603414 2.673 489 0.973332 H 3.678407 0.529431 1.143490 C 3.267407 3.546900 1.260798 H 3.030376 2.065942 2.816592 C 3.459226 3.761952 0.109140 H 3.739255 2.839801 2.036520 H 3.145899 4.392318 1.930827 C 3.525576 5.172036 0.621345 F 4.667835 5.795176 0.250121 F 2.505194 5.924029 0.127917 F 3.451695 5.236058 1.966512 C 6.769614 1.111446 1.781750 H 6.590368 1.008868 2.858992 H 5.793722 1.108211 1.287644 H 7.353666 0.255602 1.442187 C 0.166946 0.125909 0.969287 C 1.102976 0.887512 1.547783 H 0.535912 0.502635 1.784619 H 0.917302 0.868127 0.696330 H 1.446627 0.435110 2.476307 C 0.870 886 2.369542 1.753856 H 0.517558 2.854893 0.840291 H 1.797009 2.857711 2.085533 O 0.127589 2.479749 2.800293 C 0.691678 3.668339 3.152283 O 1.565089 3.661114 3.988217 C 0.186756 4.925457 2.4 73743 H 0.451533 4.932461 1.411222 H 0.902435 5.014477 2.546245 H 0.659770 5.782179 2.953493 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8422162500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.88586566 00 a.u Ru 2.112322 0.586725 0.294438 O 0.592938 2.188413 1.913698 O 1.523797 1.587736 2.117538 N 4.513708 0.593461 0.812488 N 3.038629 0.884418 2.401022 C 3.210470 0.378960 1.142952 C 5.232004 1.441898 1.767954 C 4.928168 0.397555 0.576735 C 4.742970 1.706568 1.392681 C 5.075620 1.458883 2.876412 C 6.537649 0.980405 2.992602 C 6.720405 0.323126 2.186968 C 6.400308 0.059091 0.69767 8 C 5.767081 1.401320 2.742439 C 4.295078 0.925037 2.623752 C 3.999832 0.690786 1.133394 C 4.125280 0.378821 3.429241 C 1.871701 0.865289 3.238477 C 1.024785 1.993451 3.246633 C 0.111505 1. 968542 4.061238 C 1.355353 3.245498 2.464951 C 4.303289 1.381908 2.985351 C 1.647819 0.208781 4.123152 C 0.406391 0.879906 4.889649 C 0.497582 0.185819 4.919804 C 2.626307 1.352933 4.283211 C 1.662018 0.854165 5.728861 H 4.185275 1.637539 0.576016 H 6.231493 1.052746 1.978354 H 5.335948 2.464196 1.378829 H 3.704626 2.048396 1.284162 H 5.392381 2.495164 0.986956 H 4.947549 2.395170 3.435401 H 7.222190 1.756456 2.621750 H 6.792938 0.806768 4.046211 H 7.759776 0.665951 2.270261 H 6.552546 0.969459 0.102469 H 7.080151 0.709902 0.302477 H 5.903387 2.346240 2.198733 H 6.005690 1.602995 3.795746

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236 H 3.621748 1.688479 3.015174 H 3.082808 0.717544 3.376931 H 4.344236 0.191795 4.488957 H 0.776980 2.829306 4.059706 H 2.054765 3.879920 3.027185 H 1.822963 3.030 107 1.501015 H 0.457704 3.845578 2.286501 H 4.151265 2.353464 3.463145 H 4.664516 0.678779 3.746997 H 0.305701 1.027245 5.582126 H 3.229060 1.214105 5.190788 H 2.099254 2.306579 4.390938 H 3.314635 1.439368 3.439209 H 2.443422 0.251900 5.247862 H 1.476013 0.411634 6.713355 H 2.066260 1.860424 5.877887 N 0.442408 2.137424 2.614254 O 0.508949 2.579039 3.756460 C 3.144260 4.966754 0.071264 H 3.379337 5.544789 0.821577 C 3.929078 5.389530 1.283006 H 3.875348 4.661871 2.097344 H 3.549960 6.343372 1.667443 O 5.293896 5.682199 0.933097 C 6.248477 4.707144 0.845978 O 7.331205 5.011724 0.409160 C 0.226166 3.358721 1.483036 C 1.702338 3.115001 1.089260 C 0.438602 0.940560 1.241924 C 0.182532 2.035634 2.144627 H 0.118446 4.230228 2.137334 H 0.258051 1.973637 3.147616 C 1.779673 1.596386 0.743174 H 1.920321 1.452178 0.333676 C 2.209784 4.011108 0.005254 C 0.478681 0.578529 0.073215 H 2.309181 3.236895 1.992567 H 0.682640 0.038123 1.802065 H 1.72 8904 3.862420 0.974475 H 0.642319 1.437654 0.578432 H 1.265446 1.923907 2.258390 H 0.382151 3.551190 0.589101 O 2.927531 1.103617 1.451532 C 3.530667 0.083601 1.131220 C 3.458432 0.718276 0. 115371 C 4.313158 0.645499 2.150281 C 4.147269 1.913980 0.325944 H 2.874132 0.299613 0.925599 C 5.006420 1.827935 1.930260 H 4.351174 0.143469 3.111431 C 4.921518 2.474639 0.691987 H 4.057018 2.422171 1.281097 H 5.599721 2.262186 2.727802 C 5.698272 3.733898 0.438358 F 6.881538 3.486144 0.174927 F 5.985452 4.391998 1.584663 F 5.025358 4.592890 0.363790 C 5.907746 3.317151 1.34629 9 H 5.732009 3.329065 2.428884 H 5.010533 2.907512 0.873600 H 6.759040 2.668769 1.137703 C 0.058216 0.690163 0.778350 C 1.198854 1.757284 1.040600 H 0.235122 0.326230 1.765266 H 0.759608 1. 191529 0.265378 H 1.565850 1.694846 2.060540 C 0.816476 3.195205 0.736419 H 0.383864 3.297725 0.255166 H 1.688759 3.852321 0.833063 O 0.130032 3.571169 1.767115 C 1.342197 4.143771 1.504764 O 2.160125 4.154739 2.396359 C 1.573684 4.760938 0.141880 H 1.572835 4.007226 0.652508 H 0.791646 5.491547 0.095026 H 2.546539 5.251265 0.160173 20* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8179164600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8590411300 a.u Ru 1.557195 0.814103 0.289199 O 0.611177 2.536480 2.925968 O 0.266432 1.512626 1.176622 N 3.621526 1.487305 1.630812 N 3.899 586 0.662247 1.319819 C 3.150130 0.417212 0.952737 C 4.593133 1.133662 2.670495 C 2.869128 2.744005 1.541004 C 1.706300 2.757120 2.567173 C 0.862088 4.035203 2.395621 C 1.762918 5.267388 2.6 18400 C 2.914917 5.254785 1.592882 C 3.762992 3.977295 1.792078 C 2.326490 5.279607 0.166617 C 1.432160 4.032594 0.062694 C 2.320814 2.778825 0.091567 C 0.282684 4.059879 0.967040 C 3.842211 1.996490 0.789172 C 3.195239 2.997332 1.548105 C 3.099841 4.284355 1.015300 C 2.679383 2.724852 2.943330 C 5.004453 0.278144 2.226568 C 4.493825 2.320794 0.414602 C 3.645826 4.610400 0.233452 C 4.352971 3.621861 0.918094 C 5.408251 1.365146 1.145368 C 3.478400 5.994693 0.814850 H 3.187974 2.911720 0.567397

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237 H 5.432775 1.832409 2.691793 H 4.119446 1.133788 3.662685 H 1.077979 1.8 66447 2.414833 H 2.105058 2.694973 3.590397 H 0.047697 4.033907 3.132039 H 2.163755 5.266653 3.642231 H 1.173142 6.186757 2.507252 H 3.555434 6.132851 1.747290 H 4.611433 3.965338 1.094827 H 4.174778 3.964267 2.812639 H 3.133992 5.304469 0.577508 H 1.736076 6.195981 0.027184 H 1.030241 4.071509 1.077754 H 0.389436 3.207669 0.810458 H 0.321977 4.965735 0.825817 H 2.593313 5.055055 1.593015 H 3.500935 2.729184 3.673093 H 2.186292 1.752466 3.026950 H 1.972758 3.498894 3.257055 H 5.091596 0.983287 3.056941 H 5.954341 0.277296 1.675698 H 4.813666 3.858136 1.874625 H 6.4 45306 1.717852 1.071552 H 5.151438 1.319701 2.206794 H 5.372760 0.353347 0.736431 H 2.515144 6.091171 1.332870 H 4.262515 6.219474 1.544464 H 3.505345 6.763812 0.035035 N 0.396759 2.250324 2.264217 O 1.538850 2.595661 2.567433 C 2.679741 4.899957 1.056552 H 2.304319 5.730644 0.460188 C 3.958779 5.213473 1.785604 H 4.478842 4.316295 2.133493 H 3.753089 5.835246 2.664432 O 4.82883 2 6.037895 0.988997 C 5.644488 5.518253 0.023873 O 6.279474 6.284985 0.657498 C 1.208582 2.226080 2.993238 C 2.278477 2.517712 1.886367 C 0.957212 0.506042 1.293105 C 0.800468 0.748458 2.808 307 H 1.598184 2.430279 3.995089 H 1.491213 0.093818 3.348536 C 2.315349 1.221352 1.017137 H 2.492103 1.413958 0.046317 C 1.971079 3.764189 1.098177 C 0.192656 1.133260 0.503349 H 3.266712 2.600100 2.343636 H 1.060091 0.556451 1.045081 H 1.044546 3.733187 0.524425 H 0.913481 1.700141 1.084313 H 0.210707 0.537674 3.173396 H 0.343251 2.883227 2.852393 O 3.407296 0.468986 1.560914 C 4.060649 0.493597 0.836286 C 3.571122 1.100439 0.323632 C 5.307116 0.874769 1.358809 C 4.339379 2.078402 0.959940 H 2.591973 0.872334 0.725820 C 6.062593 1.845883 0.718022 H 5.660248 0.394 631 2.265958 C 5.582758 2.451765 0.450778 H 3.934846 2.559755 1.842558 H 7.024276 2.140329 1.126115 C 6.431854 3.459283 1.169035 F 7.322139 2.867809 2.004734 F 7.160509 4.209206 0.306192 F 5.696803 4.306671 1.920266 C 5.724916 4.010093 0.116568 H 6.139707 3.549988 0.787943 H 4.738798 3.568749 0.291796 H 6.381267 3.785759 0.957545 C 0.256889 1.254053 0.853171 C 2.630015 0.528555 1.735451 H 1.013197 1.884489 1.311447 H 0.510952 0.845403 1.500900 H 3.711404 0.708466 1.699935 C 2.202326 0.122203 3.122941 H 1.141307 0.122343 3.195508 H 2.412027 0.956285 3.804524 O 3.010595 1.029070 3.463573 C 3.021241 1.571167 4.715326 O 3.734525 2.525635 4.914095 C 2.139132 0.935699 5.769898 H 1.088468 0.921155 5.460141 H 2.435256 0.102118 5.959825 H 2.238419 1.511334 6.690328 TS34* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8339992800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8676692600 a.u Ru 1.237756 0.976830 0.260054 O 0.905594 2.329949 2.462141 O 0.613871 1.854403 0.976404 N 3.731405 1.550114 1.134837 N 3.900831 0.594950 0.754213 C 3.104237 0.500547 0.538933 C 4.911616 1.177214 1.920632 C 3.028375 2.822450 1.322642 C 2.353512 2.872706 2.717014 C 1.52 8575 4.166377 2.855507 C 2.464969 5.382187 2.702903 C 3.142795 5.338021 1.317697 C 3.976811 4.040197 1.197387 C 2.054361 5.376319 0.223828 C 1.121807 4.145955 0.367099 C 1.985909 2.881723 0.195886

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238 C 0.449861 4.190393 1.754137 C 3.836970 1.913657 0.188939 C 3.284311 2.965678 0.947944 C 3.277227 4.253723 0.400238 C 2.760640 2.766415 2.353270 C 5.170484 0.248058 1.431453 C 4.4656 34 2.173198 1.047895 C 3.830838 4.529452 0.853379 C 4.432055 3.478213 1.552052 C 5.190726 1.103500 1.836168 C 3.773529 5.920497 1.439940 H 2.550246 2.986743 0.747575 H 5.749721 1.852124 1.72 8179 H 4.685376 1.210566 2.994736 H 1.709544 1.993306 2.832037 H 3.116142 2.830221 3.507814 H 1.053937 4.187921 3.845749 H 3.223193 5.378366 3.499174 H 1.893668 6.313803 2.810910 H 3.812753 6.200548 1.206718 H 4.495396 4.002273 0.230403 H 4.744689 4.025313 1.985080 H 2.513618 5.382579 0.773458 H 1.473124 6.304756 0.313835 H 0.353249 4.192621 0.408626 H 0.231659 3.339454 1.871593 H 0.157363 5.101335 1.844955 H 2.839939 5.065199 0.979241 H 3.450301 3.207901 3.084963 H 2.645218 1.710321 2.604043 H 1.793805 3.262638 2.494274 H 5.377728 0.955407 2.239585 H 5.999068 0.296121 0.714331 H 4.880732 3.668809 2.523992 H 6.273798 1.165964 1.663921 H 5.015616 1.238629 2.907151 H 4.867118 0.095368 1.565586 H 2.863711 6.058587 2.038955 H 4.627022 6.112773 2.098164 H 3.766203 6.686445 0.657282 N 0.302627 2.425303 2.108659 O 1.161605 3.003761 2.757733 C 1.905636 4.299282 2.300471 H 1.349650 5.147458 1.902780 C 3.138544 4.695572 3.066955 H 3.829329 3.861 194 3.217185 H 2.863390 5.076418 4.057103 O 3.800652 5.812708 2.447711 C 4.664356 5.659344 1.399609 O 5.104668 6.652819 0.876085 C 1.103600 1.043831 3.641708 C 2.007031 1.760342 2.584612 C 1.065870 0.346681 1.622039 C 0.993921 0.420707 3.173595 H 1.521414 1.128432 4.649629 H 1.852809 1.000281 3.527980 C 2.201346 0.710603 1.446936 H 2.241249 1.161848 0.450467 C 1.428778 3.063501 2.100396 C 0.325611 0.000664 1.090418 H 2.999437 1.930661 3.007925 H 1.393276 1.290568 1.181681 H 0.495501 2.980368 1.542693 H 0.836030 0.745397 1.707447 H 0.088588 0.915268 3.538350 H 0.114 386 1.514981 3.673924 O 3.479210 0.116274 1.723708 C 4.191327 0.531049 0.747601 C 3.668472 0.954782 0.477767 C 5.537063 0.779752 1.060278 C 4.493655 1.625893 1.382156 H 2.621873 0.833921 0.7 23277 C 6.350974 1.440652 0.150902 H 5.920257 0.448889 2.020407 C 5.833593 1.867367 1.079365 H 4.066011 1.986220 2.311911 H 7.389811 1.635460 0.397276 C 6.735297 2.536769 2.074957 F 7.403409 1.635879 2.838857 F 7.679310 3.295538 1.467489 F 6.055511 3.337178 2.923268 C 5.040739 4.252487 0.975245 H 5.576590 3.728338 1.775309 H 4.158432 3.657026 0.720616 H 5.693878 4.328036 0.105734 C 0.456303 1.223030 0.683545 C 0.747136 0.445932 1.838815 H 0.583198 1.472446 0.505593 H 1.173815 1.964462 0.348310 H 0.119104 0.038390 2.355584 C 1.876769 0.766134 2.774724 H 2.267556 0.1 34355 3.254885 H 2.681717 1.298605 2.279928 O 1.320167 1.624528 3.814798 C 2.202014 2.141044 4.694063 O 3.403132 1.968043 4.634086 C 1.494144 2.944809 5.760922 H 0.801542 3.660766 5.308264 H 0.902947 2.273792 6.393883 H 2.231030 3.465760 6.373497 TS35* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8213705100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8582077400 a.u Ru 1.119975 1.192644 0.361909 O 1.542868 0.098201 2.214938 O 0.649781 1.937424 1.377569 N 3.220800 2.275737 1.330644

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239 N 3.800127 0.172812 1.177891 C 2.882774 1.096299 0.744855 C 4.331674 2.189791 2.283753 C 2.315390 3.425449 1.284819 C 1.474810 3.506789 2.588150 C 0.455696 4.657389 2.490555 C 1.211644 5.986414 2.286000 C 2.045198 5.910346 0.989780 C 3.075474 4.762758 1.107716 C 1.101475 5.652679 0.203365 C 0.346709 4.312482 0.003650 C 1.391288 3.187256 0.086932 C 0.480160 4.394050 1.295131 C 4.082168 1.147037 0.684593 C 3.577828 2.271262 1.368649 C 3.885398 3.545811 0.878300 C 2.802055 2.15 2538 2.660950 C 4.827727 0.755781 2.070138 C 4.994440 1.306301 0.381262 C 4.711832 3.733336 0.233787 C 5.272864 2.601364 0.832766 C 5.717199 0.139332 1.020905 C 4.992786 5.117515 0.769504 H 2.023783 3.232604 0.842384 H 5.097732 2.940525 2.067729 H 3.974332 2.356572 3.306992 H 0.959034 2.550562 2.736934 H 2.135431 3.665684 3.452092 H 0.125677 4.702555 3.421117 H 1.864354 6.188556 3.147355 H 0.498203 6.818726 2.223523 H 2.584335 6.855102 0.841837 H 3.701479 4.712022 0.206628 H 3.742810 4.953457 1.961053 H 1.672574 5.626916 1.141813 H 0.382040 6.478397 0.292816 H 0.315736 4.127388 0.850717 H 1.036808 3.460549 1.444827 H 1.222682 5.199340 1.213871 H 3.483666 4.415098 1.395655 H 3.448268 2.404322 3.512839 H 2.423387 1.141783 2.825012 H 1.958297 2.849665 2.687017 H 4.892953 0.178533 2.998025 H 5.808398 0.722601 1.583187 H 5.945733 2.721057 1.678860 H 6.732729 0.051657 0.611158 H 5.806411 0.285638 2.100664 H 5.207179 0.812218 0.851214 H 4.24 1117 5.411867 1.513791 H 5.970949 5.166534 1.258814 H 4.971244 5.868633 0.027141 N 1.541283 1.348490 2.132245 O 2.352311 2.059291 2.718044 C 0.799389 4.579304 1.750742 H 0.016585 5.203920 1. 321667 C 1.818001 5.352220 2.544327 H 2.741240 4.788618 2.708729 H 1.414646 5.612489 3.529627 O 2.090401 6.630984 1.944481 C 2.954462 6.774721 0.894712 O 3.059091 7.865863 0.391288 C 1.107274 1.329030 3.235474 C 1.701498 2.214475 2.082062 C 1.248697 0.075975 1.215119 C 1.244962 0.141772 2.773850 H 1.632976 1.506262 4.178629 H 2.201180 0.559887 3.100406 C 2.149746 1.183676 1.00858 8 H 2.144272 1.570949 0.014019 C 0.746383 3.253937 1.557948 C 0.209841 0.004655 0.787623 H 2.612501 2.704409 2.432840 H 1.729481 0.943203 0.758167 H 0.091250 2.878761 0.972230 H 0.788109 0. 684412 1.409730 H 0.450580 0.781989 3.170808 H 0.058178 1.587637 3.410494 O 3.490789 0.868631 1.424275 C 4.421209 0.250472 0.631644 C 4.275013 0.019599 0.729851 C 5.611971 0.093149 1.293632 C 5.317125 0.642189 1.420279 H 3.366401 0.224194 1.265570 C 6.645721 0.699737 0.595169 H 5.702324 0.125817 2.352983 C 6.503207 0.981490 0.770225 H 5.179453 0.877551 2.469821 H 7.562329 0.968160 1.110977 C 7.645428 1.593993 1.525258 F 8.552022 0.662400 1.916785 F 8.325973 2.490212 0.769396 F 7.238414 2.233388 2.642543 C 3.747311 5.563377 0.443531 H 4.417877 5.211501 1.236299 H 3.090409 4.731794 0.169512 H 4.345715 5.855983 0.419372 C 0.929263 1.074518 1.119030 C 1.367162 0.139032 2.083283 H 0.095407 1.416586 1.183859 H 1.649147 1.729835 0.637669 H 0.604851 0.19 6404 2.780396 C 2.742402 0.196912 2.690389 H 3.118958 0.789185 2.981466 H 3.462454 0.673167 2.033290 O 2.609966 0.996535 3.900835 C 3.750068 1.275668 4.563990 O 4.853507 0.925066 4.195402

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240 C 3.464716 2.069279 5.818042 H 2.894373 2.971531 5.575676 H 2.853324 1.473224 6.503920 H 4.405034 2.337187 6.301147 TS24E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8362657700 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 2907.8668681000 a.u Ru 0.570590 1.197648 0.072227 O 1.576798 1.310266 0.448611 O 1.107955 3.057908 1.678311 N 2.880293 2.308430 1.313349 N 3.721258 0.583334 0.269055 C 2.571041 1.291441 0.472186 C 4.246457 2.264648 1.840547 C 1.816706 3.133383 1.886242 C 1.395939 2.585547 3.274028 C 0.198859 3.387973 3.817812 C 0.607567 4.868400 3.957891 C 1.029088 5.418294 2.5791 17 C 2.239274 4.612774 2.049461 C 0.157907 5.293442 1.601180 C 0.562678 3.803626 1.449421 C 0.651105 3.038629 0.889317 C 0.978219 3.257730 2.830578 C 4.001961 0.460540 0.678136 C 4.008327 1 .797785 0.242519 C 4.310637 2.806090 1.168412 C 3.771248 2.166692 1.204537 C 4.882279 1.162247 0.983159 C 4.395868 0.121057 1.991791 C 4.654239 2.505749 2.488598 C 4.706937 1.160034 2.873691 C 4.469722 1.315099 2.461021 C 4.995824 3.602051 3.471442 H 0.970381 3.546420 0.046111 H 4.747073 3.230613 1.727210 H 4.240211 2.008717 2.907830 H 1.132499 1.526728 3.167720 H 2.240111 2.647674 3.975892 H 0.089196 2.989265 4.799915 H 1.433488 4.966717 4.677006 H 0.232026 5.455441 4.353570 H 1.320889 6.472176 2.675971 H 2.571612 5.008927 1.080920 H 3.080820 4.709137 2.751644 H 0.108430 5.708394 0.620368 H 1.009488 5.878782 1.975824 H 1.404430 3.737548 0.757334 H 1.285933 2.208191 2.744013 H 1.845977 3.816667 3.206855 H 4.279220 3.841433 0.838518 H 3.567281 3.23 6036 1.301148 H 4.664973 1.957896 1.809356 H 2.951267 1.599377 1.653531 H 5.385896 0.392943 1.576023 H 5.605968 1.559554 0.262692 H 4.999733 0.907983 3.891168 H 5.093599 1.931879 1.803935 H 4.904594 1.363904 3.463660 H 3.484379 1.790621 2.509583 H 4.759291 4.589155 3.063309 H 4.446085 3.482101 4.412564 H 6.064832 3.592156 3.721099 N 1.972665 2.264262 1.249072 O 3.163600 2.320349 1.552359 C 0.533982 5.302655 0.761590 H 1.507282 5.703422 1.048052 C 0.289679 6.222628 0.101625 H 0.076773 6.215835 1.134847 H 0.211254 7.256762 0.252968 O 1.665075 5.824593 0.207130 C 2.58 0949 6.174818 0.734712 O 3.696256 5.709997 0.650634 C 2.172994 7.142865 1.827723 H 1.917977 8.124211 1.411549 H 1.303423 6.774159 2.380998 H 3.018418 7.256390 2.506336 C 0.260661 2.460133 3. 152533 C 1.038261 3.184366 2.013472 C 1.084683 0.704463 1.647220 C 0.763424 1.003158 3.140727 H 0.418209 2.944557 4.121319 H 1.696447 0.917468 3.708150 C 1.769649 2.042432 1.226922 H 1.785196 2.207289 0.146015 C 0.177719 4.076747 1.158068 C 0.212163 0.358184 0.933343 H 1.841756 3.792089 2.438883 H 1.797466 0.113498 1.535868 H 0.794718 3.688062 0.854758 H 1.027845 1.044089 1.185431 H 0.045890 0.301581 3.576646 H 0.818317 2.497319 2.957997 O 3.118465 2.087417 1.723799 C 4.179347 1.673023 0.960534 C 4.102837 0.717069 0.056229 C 5.413435 2.255875 1.288526 C 5.2615 35 0.358968 0.747987 H 3.178942 0.199457 0.283080 C 6.559112 1.894396 0.593035 H 5.449208 2.987157 2.089847 C 6.488206 0.945782 0.435630 H 5.195161 0.408509 1.511333 H 7.512926 2.344375 0.84 9900 C 7.721496 0.608213 1.220282 F 7.947870 1.502851 2.216510 F 8.832083 0.617559 0.443500

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241 F 7.643915 0.607794 1.801618 C 0.239109 0.829907 1.285160 C 0.966010 0.155995 1.986558 H 0.759613 1.730034 0.973487 H 0.829429 0.928935 1.451405 H 2.028636 0.019827 2.088575 C 0.392954 0.893948 3.173768 H 0.659825 1.143019 3.045953 H 0.495932 0.262145 4.069150 O 1.196112 2.071687 3.349328 C 0.841544 3.088184 4.191362 O 1.608884 4.012507 4.312400 C 0.492676 2.993674 4.898317 H 1.299093 3.102483 4.165011 H 0.622239 2.035602 5.413302 H 0.551217 3.806668 5.622614 TS25E* B3LYP/SDD/6 31 G(d) SCF energy in gas p hase: 2908.8232382500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8571922600 a.u Ru 0.634864 1.480466 0.130566 O 1.473818 1.388535 0.676083 O 1.619334 3.266736 1.829232 N 2.816195 2. 812006 1.233042 N 3.756042 1.041198 0.353444 C 2.566023 1.688941 0.515027 C 4.168234 2.856424 1.795890 C 1.666236 3.581257 1.717213 C 1.131572 2.954289 3.031756 C 0.143244 3.681876 3.494320 C 0.188835 5.169348 3.733586 C 0.716330 5.795865 2.426417 C 2.006257 5.062870 1.985053 C 0.367706 5.664732 1.336523 C 0.689823 4.168728 1.079766 C 0.606125 3.484555 0.589663 C 1.212137 3.54720 4 2.391411 C 4.014565 0.212388 0.300983 C 3.974025 1.394644 0.470930 C 4.196714 2.620730 0.161388 C 3.772717 1.355860 1.970545 C 4.883544 1.794674 0.947085 C 4.402078 0.254926 1.654763 C 4.497029 2.700193 1.527564 C 4.612317 1.507953 2.245504 C 4.664373 0.983126 2.486751 C 4.737600 4.037680 2.188340 H 0.985197 4.069386 0.258190 H 4.613283 3.849316 1.692763 H 4.157799 2.594383 2.863653 H 0.917271 1.890182 2.858078 H 1.904762 3.003235 3.812649 H 0.504378 3.228668 4.427257 H 0.936666 5.266085 4.533717 H 0.708581 5.706258 4.068547 H 0.951300 6.855075 2.594191 H 2.414 760 5.518457 1.073133 H 2.770335 5.157582 2.771639 H 0.033222 6.138690 0.404163 H 1.275894 6.195561 1.655707 H 1.452861 4.107153 0.302909 H 1.466861 2.489030 2.239113 H 2.137999 4.050385 2.7 01123 H 4.147495 3.539514 0.417149 H 3.521979 2.350032 2.352368 H 4.694525 1.042837 2.480401 H 2.989414 0.657666 2.279780 H 5.523958 1.131097 1.534248 H 5.493712 2.243218 0.152505 H 4.883777 1.544463 3.299003 H 4.433807 1.907722 1.952212 H 5.723215 1.021662 2.773122 H 4.081099 0.973257 3.414280 H 4.324283 4.852068 1.587788 H 4.290338 4.072261 3.188201 H 5.812919 4.225841 2.309672 N 2.182642 2.267917 1.354198 O 3.383638 2.030410 1.494889 C 0.450266 5.503417 0.874578 H 1.385678 5.887116 1.283911 C 0.325359 6.488248 0.036716 H 0.068767 6.530952 0.985088 H 0.239355 7.4 99206 0.451157 O 1.706054 6.126123 0.132018 C 2.631161 6.397600 0.826018 O 3.751082 5.958633 0.683944 C 2.228085 7.255121 2.009490 H 1.955572 8.267039 1.688341 H 1.370780 6.825754 2.537332 H 3.081903 7.317207 2.684298 C 0.013208 2.506193 2.996049 C 0.872629 3.282663 1.971175 C 0.802959 0.867552 1.380696 C 0.375296 1.018283 2.856180 H 0.126808 2.876950 4.016055 H 1.232642 0.789655 3.497225 C 1.628937 2.172572 1.166968 H 1.769265 2.421234 0.110371 C 0.084911 4.240636 1.116856 C 0.405169 0.805254 0.439801 H 1.651746 3.845963 2.492340 H 1.457762 0.007024 1.220643 H 0.8 46188 3.870458 0.687180 H 1.354189 1.091718 0.879643 H 0.439702 0.343187 3.138608 H 1.073201 2.647570 2.754856 O 2.909687 2.077883 1.808756 C 4.030179 1.716964 1.103966

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242 C 4.033146 0.837477 0 .017519 C 5.234669 2.264524 1.570955 C 5.242190 0.523723 0.605215 H 3.130917 0.343142 0.321299 C 6.432060 1.947753 0.943361 H 5.206899 2.935031 2.424038 C 6.440730 1.078913 0.155104 H 5.235651 0.186794 1.423802 H 7.362987 2.371415 1.306437 C 7.728546 0.790083 0.868977 F 7.996491 1.716861 1.824445 F 8.788042 0.798092 0.024011 F 7.713301 0.409725 1.487947 C 0.340427 0.823847 0.9375 11 C 1.254034 1.525557 1.864509 H 1.206990 1.118392 1.520388 H 0.607004 0.755054 1.462140 H 2.317018 1.430228 2.087526 C 0.462406 1.697838 3.129089 H 0.228653 2.762430 3.255178 H 0.485975 1.154557 3.109036 O 1.296792 1.218890 4.205987 C 0.928814 1.342812 5.514675 O 1.691844 0.946633 6.362309 C 0.418669 1.967673 5.814297 H 0.477143 2.994443 5.436425 H 1.233749 1.405829 5.344762 H 0.558565 1.972798 6.895414 TS26E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8214079500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8557816600 a.u Ru 1.702515 0.529963 0.071306 O 1.240092 2.197495 1.37438 2 O 0.306983 3.340829 0.294357 N 3.812098 1.411770 0.295490 N 2.263338 2.085101 1.687043 C 2.556646 1.142053 0.744096 C 4.340086 2.692580 0.772410 C 4.307958 0.684816 0.877260 C 3.827057 1. 373646 2.182176 C 4.245995 0.540321 3.408256 C 5.783638 0.419700 3.429650 C 6.263297 0.268577 2.134426 C 5.848351 0.587411 0.913013 C 5.627368 1.672777 2.045720 C 4.081726 1.551418 2.007508 C 3.704738 0.732269 0.755271 C 3.608147 0.859239 3.301627 C 1.042224 2.293706 2.413114 C 0.102678 3.210625 1.888366 C 1.082559 3.438100 2.591157 C 0.387000 3.995843 0.626215 C 3.416469 2.97041 4 1.963999 C 0.844688 1.705075 3.675221 C 1.343992 2.798584 3.811223 C 0.364554 1.956462 4.340369 C 1.904616 0.880479 4.373207 C 2.649551 3.029413 4.535662 H 4.205510 1.200293 0.104231 H 5. 390442 2.610981 1.062696 H 4.256037 3.465137 0.005664 H 2.732992 1.479056 2.149504 H 4.245348 2.388688 2.249246 H 3.901489 1.041602 4.322715 H 6.242354 1.414349 3.524840 H 6.102951 0.163970 4.303310 H 7.357429 0.357106 2.147983 H 6.209811 0.130975 0.018329 H 6.309211 1.583618 0.991883 H 5.989215 2.194920 1.148921 H 5.940387 2.273378 2.911670 H 3.629802 2.546363 1.948155 H 2.514083 0.788263 3.306249 H 3.888698 1.465004 4.174173 H 1.804216 4.145294 2.187465 H 0.475923 4.609408 0.354955 H 1.235044 4.678695 0.769069 H 0.646535 3.354084 0.222815 H 3.097107 4.013170 2.033238 H 3.880135 2.689161 2.918933 H 0.530487 1.491255 5.310377 H 2.747631 0.639737 3.722607 H 2.298600 1.428201 5.239161 H 1.496688 0.061691 4.756017 H 2.989621 4.064284 4.423356 H 3.442 048 2.384265 4.134034 H 2.560142 2.810721 5.604758 N 0.216512 3.015658 1.376183 O 0.178001 3.430927 2.470477 C 4.533614 3.435166 2.031511 H 5.067243 3.134492 2.933767 C 5.205699 4.517293 1.2 26204 H 6.129825 4.143026 0.770589 H 5.489293 5.364056 1.863559 O 4.409623 4.954927 0.114858 C 3.411978 5.864384 0.266572 O 2.625522 6.010334 0.643613 C 3.349701 6.668696 1.549482 H 4.264163 7.254582 1.695476 H 3.225417 6.013967 2.418190 H 2.499031 7.346843 1.480504 C 1.240337 2.064723 2.848226 C 2.705587 1.739423 2.454630 C 1.121932 0.021374 1.600266 C 0.526237 0.703985 2.826012 H 1.179913 2.569616 3.818071 H 0.775856 0.133769 3.728277

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243 C 2.628350 0.413449 1.632169 H 3.027384 0.536652 0.619193 C 3.385994 2.840663 1.694078 C 0.483639 0.361930 0.273598 H 3.280766 1.5 01318 3.356034 H 1.096033 1.101475 1.723987 H 2.890031 3.151882 0.774384 H 0.308012 1.423152 0.122376 H 0.565001 0.791401 2.792617 H 0.793968 2.743469 2.109151 O 3.424163 0.563979 2.324353 C 4.004092 1.550605 1.552133 C 5.127893 1.249532 0.772582 C 3.497929 2.852492 1.593223 C 5.747475 2.252783 0.033355 H 5.511700 0.233447 0.763891 C 4.123661 3.853095 0.850337 H 2.614914 3.076872 2.183049 C 5.245414 3.558183 0.070623 H 6.618151 2.024779 0.572881 H 3.722300 4.860773 0.865429 C 5.950220 4.651989 0.680332 F 6.911880 5.241781 0.071437 F 5.103214 5.631865 1.065320 F 6.563930 4.185979 1.793978 C 0.595737 0.418575 0.861731 C 1.666239 1.381937 1.558362 H 0.514057 0.030150 1.845252 H 0.998696 1.424995 0.798877 H 1.661851 0.843981 2.510276 C 1.699813 2.874528 1.788998 H 2.007595 3.435209 0.910137 H 0.702630 3.228005 2.074510 O 2.561304 3.104156 2.926215 C 3.778275 3.712045 2.831651 O 4.487133 3.721135 3.809391 C 4.164317 4.371725 1.520240 H 4.22 9501 3.646723 0.701980 H 3.437633 5.137600 1.227566 H 5.139423 4.838407 1.662249 TS27E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8331500500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8575346100 a.u Ru 1.490366 0.474673 0.199381 O 1.734983 1.181128 1.643169 O 1.423755 0.783114 2.500827 N 2.649314 2.965323 0.725206 N 0.657006 2.948774 1.628861 C 1.510888 2.231378 0.828713 C 2.538197 4.309799 1.296816 C 3.707080 2.565561 0.208806 C 3.555336 3.301330 1.565196 C 4.645883 2.826218 2.548040 C 6.040055 3.101758 1.952436 C 6.181346 2.341061 0.618230 C 5.112598 2.866888 0.366742 C 5.99 0707 0.827118 0.865069 C 4.573307 0.559309 1.444549 C 3.558877 1.040701 0.376655 C 4.476319 1.314563 2.790452 C 0.639995 2.597685 2.130697 C 1.779514 3.091105 1.460157 C 3.046278 2.782208 1. 966395 C 1.648898 3.973521 0.238062 C 1.292776 4.166293 2.174848 C 0.771321 1.885463 3.339592 C 3.209459 2.022862 3.131871 C 2.060456 1.594086 3.803393 C 0.421188 1.478627 4.178015 C 4.587537 1.714020 3.670646 H 3.905824 0.605413 0.569367 H 3.430324 4.577638 1.868374 H 2.400183 5.058132 0.504067 H 2.560840 3.098762 1.979289 H 3.639624 4.387496 1.413728 H 4.534716 3.368422 3.496474 H 6.184075 4.179956 1.790486 H 6.818596 2.777862 2.656374 H 7.177066 2.521699 0.191895 H 5.214979 2.383211 1.347273 H 5.260069 3.947353 0.515524 H 6.130338 0.271829 0.072282 H 6.7593 69 0.470722 1.565611 H 4.451289 0.517495 1.615094 H 3.526262 1.127304 3.292198 H 5.270452 0.957031 3.461237 H 3.931084 3.148991 1.451199 H 2.627317 4.141278 0.222029 H 1.240515 4.958287 0.50 1211 H 0.980587 3.549096 0.518092 H 0.614161 5.021254 2.108883 H 1.547921 4.013600 3.232179 H 2.165749 1.027724 4.727410 H 1.360437 1.523301 3.623507 H 0.518734 2.139404 5.049716 H 0.305505 0.460764 4.566554 H 5.361853 1.901292 2.921577 H 4.660723 0.670213 3.998019 H 4.812599 2.339641 4.544834 N 1.637079 0.461070 2.710643 O 1.735016 0.939135 3.828381 C 6.280979 0.042364 1.862277 H 6.495751 0.570555 2.791933 C 7.487342 0.258032 1.010803 H 7.909669 0.664919 0.596533 H 8.279974 0.726760 1.607396 O 7.174205 1.056690 0.139965

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244 C 7.053389 2.408484 0.060270 O 6.590895 3.00 0371 1.010324 C 7.531098 3.108587 1.196304 H 8.605854 2.956537 1.347909 H 7.008032 2.733086 2.081455 H 7.336480 4.175008 1.081616 C 3.012188 1.287573 2.729908 C 3.802092 0.006825 2.368666 C 1.346951 0.251933 1.840097 C 1.575331 0.797267 2.953258 H 3.439074 1.801379 3.597895 H 1.496359 0.310522 3.932594 C 2.767798 0.896795 1.640604 H 3.005188 0.987053 0.575312 C 5.025026 0.277282 1.540908 C 0.833138 0.346232 0.534165 H 4.079722 0.518222 3.290452 H 0.676396 1.049361 2.163882 H 4.841560 0.789777 0.595720 H 1.140103 1.368846 0.343960 H 0.832174 1.596321 2.930389 H 3.04 7713 1.995128 1.889892 O 2.848088 2.211203 2.236793 C 2.256389 3.221752 1.519238 C 2.785348 3.636312 0.288171 C 1.127645 3.856686 2.046436 C 2.156796 4.647980 0.430351 H 3.685642 3.164771 0.093777 C 0.502570 4.873154 1.325391 H 0.737730 3.533624 3.005929 C 1.004758 5.258822 0.079848 H 2.561642 4.969650 1.384846 H 0.383139 5.354247 1.726241 C 0.269648 6.257490 0.763455 F 0.54242 3 7.052572 0.038504 F 0.520105 5.631769 1.686863 F 1.106767 7.051625 1.464424 C 0.607576 0.454312 0.590479 C 1.546313 0.587275 1.342994 H 0.825287 0.069358 1.579165 H 0.654011 1.535304 0.480 777 H 1.305991 0.298382 2.371271 C 2.036376 2.022620 1.306528 H 2.503094 2.260767 0.348240 H 1.215359 2.734950 1.483418 O 2.986008 2.109769 2.388398 C 3.827032 3.178028 2.532623 O 4.583193 3.183755 3.472869 C 3.755897 4.283462 1.498417 H 4.018295 3.909944 0.502022 H 2.752040 4.715370 1.437736 H 4.466289 5.058749 1.786650 TS28E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8350761800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8644852700 a.u Ru 1.825203 0.505077 0.119193 O 1.702300 2.448156 0.920134 O 0.382087 3.168390 0.793230 N 3.831189 1.503748 0.674069 N 2.086951 2.192216 1.8 05124 C 2.535791 1.208649 0.965924 C 4.272609 2.801408 1.193394 C 4.495289 0.809800 0.433599 C 4.364250 1.633375 1.741937 C 4.971378 0.848463 2.920550 C 6.460553 0.567248 2.632071 C 6.587662 0.256977 1.333686 C 5.994841 0.551200 0.154913 C 5.825861 1.589021 1.502088 C 4.326275 1.307465 1.782341 C 3.766062 0.531526 0.579221 C 4.207464 0.480694 3.078314 C 0.798236 2.341807 2.419760 C 0.168486 3.150295 1.782256 C 1.424125 3.297603 2.380907 C 0.152236 3.933502 0.527481 C 3.160418 3.130763 2.195414 C 0.553841 1.806522 3.699142 C 1.724313 2.699415 3.611597 C 0.717005 1.981734 4.261374 C 1.632354 1.121596 4.512183 C 3.098773 2.839443 4.223328 H 3.988974 1.133587 0.338261 H 5.257543 2.730313 1.662541 H 4.330213 3.542771 0.385081 H 3.301796 1.839599 1.926348 H 4.876105 2.600290 1.633392 H 4.879413 1.446773 3.837306 H 7.014088 1.513062 2.540115 H 6.907119 0.016229 3.470614 H 7.646862 0.457955 1.126474 H 6.100216 0.005551 0.785088 H 6.544045 1.498 308 0.043200 H 5.926789 2.205795 0.600023 H 6.262470 2.160780 2.333364 H 3.785864 2.249858 1.889880 H 3.151245 0.288008 3.305575 H 4.618914 1.051076 3.922536 H 2.171974 3.913411 1.885561 H 0.747535 4.417440 0.138146 H 0.876307 4.730880 0.743886 H 0.595582 3.318183 0.260927 H 2.812218 4.165324 2.131401 H 3.467777 2.937640 3.231372 H 0.916572 1.553995 5.242213 H 2.436265 0.713512 3.894346 H 2.087506 1.831532 5.216169

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245 H 1.216678 0.304955 5.111937 H 3.581990 3.769635 3.907972 H 3.753053 2.012722 3.916167 H 3.054326 2.828230 5.317667 N 0.816398 3.392631 1.067577 O 1.214 501 4.488912 1.474255 C 4.404516 2.594116 2.535853 H 4.828760 2.151505 3.437824 C 5.298786 3.584979 1.837173 H 6.193622 3.086797 1.446464 H 5.647565 4.358292 2.532786 O 4.678784 4.171844 0.6 84467 C 3.830071 5.228598 0.788061 O 3.160176 5.522639 0.177356 C 3.787516 6.001421 2.091244 H 4.765083 6.438728 2.323639 H 3.499712 5.353892 2.925894 H 3.055936 6.802269 1.983381 C 0.936818 1.877336 3.236766 C 2.275317 1.247091 2.779853 C 0.316538 0.148722 2.012159 C 0.045671 0.700215 3.267069 H 1.036091 2.385539 4.201909 H 0.125076 0.088605 4.161557 C 1.863630 0.054196 1.851408 H 2.120904 0.263723 0.808442 C 3.190020 2.232475 2.112083 C 0.440472 0.355397 0.807270 H 2.774186 0.801015 3.648418 H 0.122350 1.207186 2.170096 H 2.802315 2.681654 1.196887 H 0.133985 1.366424 0.513930 H 1.094136 1.012523 3.279184 H 0.608262 2.632415 2.509890 O 2.515436 1.155150 2.252495 C 3.515074 1.692302 1.492524 C 4.426506 0.930682 0.748002 C 3.623563 3.090263 1.513982 C 5.433621 1.571883 0.028067 H 4.370372 0.152263 0.748887 C 4.638465 3.718072 0.802813 H 2.880148 3.659176 2.060387 C 5.547956 2.963294 0.051677 H 6.136194 0.982654 0.553041 H 4.710831 4.800 545 0.809513 C 6.673444 3.631215 0.681205 F 7.815268 3.657441 0.051479 F 6.387265 4.914016 0.997310 F 6.976396 2.987811 1.834675 C 0.347657 0.790099 1.163087 C 0.744299 1.175046 1.947278 H 0.853858 0.141468 1.393361 H 0.876129 1.527512 0.569795 H 1.038697 0.517036 2.754741 C 1.144732 2.614552 2.168430 H 0.744110 3.264214 1.392148 H 0.776224 2.960196 3.144666 O 2.589965 2.627421 2.197851 C 3.335526 3.746366 1.947053 O 4.538206 3.626477 1.943072 C 2.613132 5.046412 1.675922 H 2.191053 5.037679 0.662973 H 1.799199 5.229119 2.384736 H 3.342709 5.854675 1.739577 12E* B3LYP /SDD/6 31G(d) SCF energy in gas p hase: 2908.8531462100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8871114200 a.u Ru 0.682860 1.333653 0.024153 O 1.456143 1.657649 0.111430 O 1.032518 3.326602 1.474359 N 3.262 805 2.163281 1.064051 N 3.741427 0.310463 0.009608 C 2.721689 1.164237 0.318367 C 4.646701 1.916488 1.475105 C 2.370083 3.123553 1.705712 C 1.959239 2.627606 3.117824 C 0.925391 3.584837 3.7 38529 C 1.544185 4.993802 3.847794 C 1.948821 5.489654 2.443706 C 2.999666 4.529570 1.838967 C 0.697828 5.533065 1.542743 C 0.076605 4.114792 1.424262 C 1.138666 3.201655 0.787349 C 0.320440 3.623940 2.831496 C 3.780785 0.756543 0.954700 C 3.739866 2.088976 0.492879 C 3.798740 3.126233 1.428387 C 3.700550 2.418709 0.982765 C 5.047860 0.789808 0.517463 C 3.988862 0.466821 2.318400 C 3.949918 2.868990 2.797178 C 4.059286 1.541301 3.215712 C 4.118726 0.943859 2.853549 C 4.042571 4.008878 3.785221 H 1.440610 3.617246 0.192417 H 5.265440 2.810730 1.362928 H 4.688338 1.5 98647 2.526137 H 1.541784 1.615884 3.030720 H 2.847989 2.559618 3.761406 H 0.650204 3.222864 4.737971 H 2.419865 4.972609 4.511973 H 0.820964 5.688419 4.295218 H 2.387570 6.492996 2.518199 H 3.322675 4.883189 0.851071 H 3.888642 4.498895 2.485906 H 0.955490 5.912182 0.545236 H 0.042446 6.225728 1.966639

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246 H 0.801406 4.170341 0.779817 H 0.779155 2.628412 2.769625 H 1.076715 4.295832 3.259112 H 3.734758 4.152617 1.075020 H 3.486376 3.479827 1.132408 H 4.673146 2.218729 1.453656 H 2.962110 1.823659 1.528004 H 5.591080 0.022657 1.007040 H 5.658903 1.153356 0.318126 H 4.2 05348 1.325218 4.272412 H 4.347561 1.672372 2.072324 H 4.914884 0.989956 3.604706 H 3.195294 1.281123 3.339632 H 3.368826 4.827729 3.511466 H 3.793197 3.682924 4.800260 H 5.058685 4.424327 3 .813588 N 1.878611 2.579000 0.944692 O 3.085190 2.638846 1.178687 C 0.809375 5.436660 1.104128 H 1.734978 5.769732 1.575387 C 0.133222 6.475188 0.246604 H 0.637814 6.568786 0.722133 H 0.180855 7.461343 0.722914 O 1.222401 6.138552 0.089433 C 2.249228 6.395613 0.762457 O 3.347482 5.966601 0.483770 C 1.980784 7.223589 2.003338 H 1.663849 8.239175 1.739929 H 1.195508 6.773383 2.6188 42 H 2.907304 7.280251 2.574810 C 0.137239 2.428453 3.142973 C 1.082789 3.165856 2.147977 C 0.994324 0.722947 1.618096 C 0.555768 0.946282 3.083753 H 0.206615 2.846141 4.152488 H 1.415542 0.773950 3.740872 C 1.790251 2.029842 1.332403 H 1.875322 2.267007 0.267154 C 0.380172 4.184798 1.292096 C 0.230330 0.506959 0.708090 H 1.883869 3.668997 2.697490 H 1.671335 0.127810 1.528968 H 0.539737 3.864725 0.801655 H 1.083950 1.087685 1.059762 H 0.243499 0.266529 3.398342 H 0.906763 2.546917 2.827193 O 3.118057 1.965462 1.889026 C 4.170357 1.477972 1.161036 C 4.069471 0.509 519 0.155802 C 5.429138 1.990082 1.514427 C 5.224027 0.070402 0.494448 H 3.126031 0.038853 0.089072 C 6.570995 1.549672 0.859654 H 5.485211 2.732066 2.304621 C 6.473958 0.589206 0.155689 H 5.136295 0.707317 1.245113 H 7.541947 1.947463 1.137668 C 7.706244 0.166524 0.899340 F 8.012059 1.029228 1.902516 F 8.793646 0.124065 0.091819 F 7.572868 1.052728 1.464064 C 0.057156 0.728791 0.863322 C 0.718786 0.377900 1.754784 H 0.576265 1.664027 1.096704 H 1.004076 0.799691 1.107131 H 1.709385 0.085328 2.082969 C 0.084585 0.807094 2.966388 H 1.051663 1.237020 2.715503 H 0.260 087 0.071425 3.609563 O 0.737319 1.737132 3.686116 C 0.234842 2.640353 4.580511 O 1.019723 3.346513 5.166418 C 1.265667 2.704556 4.766820 H 1.741523 3.077173 3.853003 H 1.693356 1.722933 4.9 98992 H 1.472811 3.392218 5.587310 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8565587100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8938957800 a.u Ru 1.448602 0.496096 0.049645 O 1.909268 1.436273 0. 917504 O 1.785462 0.582086 2.935676 N 2.429299 3.094689 0.771874 N 0.450998 2.993238 1.694939 C 1.320420 2.319052 0.883685 C 2.291599 4.423890 1.373269 C 3.468715 2.740594 0.192918 C 3.272769 3.520580 1.519843 C 4.322461 3.074444 2.555751 C 5.736604 3.337467 1.999239 C 5.929292 2.547041 0.688348 C 4.890898 3.023179 0.351632 C 5.742396 1.040594 0.963210 C 4.314504 0.778540 1.51924 1 C 3.320320 1.233821 0.441360 C 4.134246 1.571189 2.830524 C 0.879603 2.639958 2.102911 C 1.962365 3.060631 1.301526 C 3.262630 2.743714 1.706639 C 1.738072 3.879742 0.049603 C 1.030444 4. 245971 2.227231 C 1.105026 2.005102 3.339733 C 3.515080 2.047980 2.896083 C 2.424367 1.700648 3.698781 C 0.009229 1.701768 4.318597 C 4.929361 1.721304 3.318136 H 3.559221 0.692233 0.510036

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247 H 3.170495 4.686728 1.967850 H 2.160827 5.189729 0.596903 H 2.259059 3.332453 1.897934 H 3.360488 4.600184 1.333082 H 4.176505 3.644558 3.482702 H 5.883001 4.412465 1.820070 H 6.491175 3.031266 2.735878 H 6.936336 2.727821 0.290927 H 5.028262 2.497056 1.305148 H 5.024769 4.098004 0.543517 H 5.902795 0.457593 0.047229 H 6.487282 0.700295 1.695703 H 4.202561 0.291765 1.707673 H 3.144000 1.375200 3.251800 H 4.872118 1.227921 3.568071 H 4.104820 3.060694 1.096280 H 2.688054 4.074414 0.456562 H 1.287982 4.852853 0.285765 H 1.066986 3.385145 0.660200 H 0.320279 5.07 1549 2.126376 H 1.264735 4.127128 3.292723 H 2.601536 1.191297 4.644707 H 0.999442 1.753753 3.861095 H 0.009804 2.418294 5.150702 H 0.108512 0.704918 4.757464 H 5.642391 1.927008 2.515229 H 5.023070 0.667325 3.606515 H 5.224586 2.318538 4.190891 N 2.029581 1.566412 2.215519 O 2.364638 2.672051 2.647971 C 5.954152 0.198898 2.136517 H 6.074519 0.813571 3.029346 C 7.237621 0.126609 1.418357 H 7.666131 0.774200 0.963627 H 7.989484 0.513989 2.117235 O 7.051315 1.028872 0.317635 C 6.972276 2.372872 0.499766 O 6.622495 3.058667 0.435669 C 7.352475 2.948992 1.849304 H 8.402425 2.741145 2.085164 H 6.735706 2.525400 2.648320 H 7.205786 4.028337 1.806967 C 2.625237 1.118664 2.842143 C 3.448159 0.129122 2.444487 C 1.037661 0.380718 1.756175 C 1.186719 0.592400 2.950392 H 2.996389 1.576750 3.765465 H 1.060981 0.037775 3.887294 C 2.476429 0.978758 1.576541 H 2.784729 0.975288 0.523944 C 4.737655 0.188627 1.745093 C 0.520772 0.325704 0.504060 H 3.649 782 0.723602 3.343651 H 0.370445 1.200870 2.006461 H 4.642896 0.785684 0.837084 H 1.110062 1.215795 0.287098 H 0.429463 1.381781 2.941909 H 2.698714 1.879852 2.053843 O 2.560919 2.336715 2.0 69590 C 1.993623 3.306980 1.277182 C 2.613864 3.712464 0.089168 C 0.798199 3.910593 1.686532 C 2.025045 4.698160 0.701627 H 3.554329 3.255626 0.204294 C 0.211814 4.892591 0.893285 H 0.321488 3.589955 2.606346 C 0.817736 5.281709 0.306947 H 2.500674 5.011698 1.624606 H 0.730941 5.335138 1.199093 C 0.159213 6.340662 1.143788 F 0.174059 7.548569 0.536056 F 1.147034 6.049895 1.378778 F 0.754870 6.491654 2.347125 C 0.439273 0.587606 0.810599 C 0.909717 0.497895 1.601199 H 1.233607 0.235534 1.473729 H 0.607076 1.624681 0.514377 H 0.828871 0.099822 2.505811 C 1.600774 1.8 21774 1.884758 H 1.539599 2.484336 1.024856 H 1.139349 2.315068 2.753128 O 2.969930 1.527180 2.224034 C 4.021052 2.258426 1.750845 O 5.136270 1.832663 1.949766 C 3.736392 3.546111 1.006192 H 3.334684 3.322182 0.010882 H 3.012830 4.183082 1.524374 H 4.681098 4.080160 0.896257 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8506041600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8848787300 a.u Ru 1.903206 0.447793 0.053117 O 1.944382 2.056971 1.526611 O 0.002446 3.111131 1.501724 N 3.741830 1.450031 1.121148 N 1.862612 1.864828 2.161394 C 2.430104 1.092136 1.187817 C 4.074372 2.6267 52 1.928339 C 4.537271 0.988828 0.015281 C 4.435075 1.997444 1.192415 C 5.180326 1.452457 2.425042 C 6.662853 1.227919 2.061985 C 6.762947 0.220413 0.897549 C 6.028236 0.786278 0.339998 C 6 .118478 1.114506 1.324753 C 4.624808 0.893210 1.685023 C 3.923822 0.353889 0.428523

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248 C 4.533860 0.118269 2.845688 C 0.496105 1.931946 2.600310 C 0.365843 2.861685 1.977302 C 1.690957 2.948616 2.414303 C 0.132702 3.810947 0.909406 C 2.858581 2.709560 2.857077 C 0.069456 1.195699 3.721722 C 2.167255 2.161635 3.471417 C 1.268811 1.311753 4.120899 C 1.011962 0.350395 4.551684 C 3.613038 2.243412 3.902342 H 4.055349 1.084481 0.403745 H 5.012547 2.487474 2.471621 H 4.172171 3.519645 1.295159 H 3.374846 2.161641 1.428682 H 4.858552 2.966304 0.892115 H 5.106002 2.181184 3.243271 H 7.132710 2.181715 1.782089 H 7.209925 0.846747 2.934485 H 7.817282 0.058295 0.638992 H 6.113231 0.095359 1.188788 H 6.489238 1.738395 0.641591 H 6.205179 1.856188 0.519906 H 6.650 482 1.523695 2.194861 H 4.169018 1.838962 1.980273 H 3.484130 0.273814 3.127516 H 5.044098 0.286201 3.730195 H 2.355887 3.666814 1.938785 H 0.688951 4.427753 0.535181 H 0.892094 4.493485 1.3 13672 H 0.597635 3.292446 0.064553 H 2.478651 3.726423 2.985688 H 3.070684 2.294454 3.850861 H 1.608946 0.731171 4.976537 H 1.935656 0.102741 4.024035 H 1.288703 0.882652 5.471747 H 0.537196 0.587413 4.859645 H 4.040922 3.224557 3.673617 H 4.222039 1.492992 3.380964 H 3.723479 2.060366 4.976590 N 1.190825 3.058687 1.891154 O 1.701730 3.923407 2.603468 C 4.388036 3.066693 2.490616 H 4.752386 2.749479 3.468312 C 5.288354 4.027476 1.757111 H 6.230377 3.542017 1.477313 H 5.551160 4.882479 2.392582 O 4.725582 4.467257 0.512485 C 3.803244 5.464521 0.460170 O 3.167578 5.6 05104 0.561569 C 3.640879 6.367262 1.666700 H 4.581274 6.872641 1.913497 H 3.323321 5.795641 2.544969 H 2.884679 7.115299 1.428172 C 0.879349 2.230503 2.924398 C 2.296423 1.649295 2.700635 C 0.528730 0.034083 1.915573 C 0.021608 0.989445 3.002164 H 0.833892 2.863193 3.817508 H 0.084839 0.517085 3.986736 C 2.065829 0.341698 1.880357 H 2.411150 0.466419 0.848553 C 3.229580 2.602021 2.013878 C 0.103452 0.275637 0.546235 H 2.714439 1.339185 3.665740 H 0.404283 1.011087 2.193648 H 2.906960 2.928439 1.024579 H 0.105502 1.285019 0.188567 H 1.083809 1.217947 2.863576 H 0.592800 2.859510 2.070886 O 2.807307 0.735534 2.480470 C 3.617802 1.500265 1.684115 C 4.627290 0.933969 0.892647 C 3.447596 2.889147 1.719848 C 5.456558 1.758538 0.137209 H 4.767685 0.142816 0.887814 C 4.288290 3.707388 0.969687 H 2.638782 3.303005 2.312286 C 5.291574 3.146975 0.172302 H 6.236538 1.323230 0.479651 H 4.149809 4.783301 0.986646 C 6.226051 4.025987 0.607082 F 7.372 400 4.279732 0.070866 F 5.673735 5.224829 0.898960 F 6.593740 3.453888 1.779018 C 0.307245 0.791042 0.593865 C 0.896375 1.376686 1.406749 H 0.932538 0.239078 1.299252 H 0.846535 1.603451 0.1 08155 H 0.992356 0.929200 2.391805 C 1.015325 2.885449 1.499094 H 0.793260 3.362458 0.547027 H 0.315845 3.275312 2.255211 O 2.360555 3.157190 1.945307 C 3.007088 4.326021 1.669114 O 4.144795 4.449673 2.057860 C 2.270308 5.391764 0.882319 H 2.154481 5.094013 0.166752 H 1.272012 5.590435 1.285352 H 2.867173 6.303689 0.919307 TS29E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8266592400 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8613266700 a.u Ru 0.273655 1.361111 0.181703 O 1.876181 1.175615 0.501998 O 1.698048 2.887525 1.864293 N 2.423707 2.902268 1.009897

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249 N 3.523902 1.267586 0.0 68706 C 2.266516 1.767704 0.290510 C 3.813632 3.272326 1.285420 C 1.273413 3.570960 1.617187 C 1.094730 3.079862 3.078350 C 0.179433 3.693414 3.687362 C 0.058544 5.231078 3.672462 C 0.117159 5.720454 2.219561 C 1.408428 5.112416 1.621795 C 1.109236 5.285298 1.389613 C 1.224173 3.738375 1.392821 C 0.061366 3.171865 0.768796 C 1.393008 3.250340 2.845777 C 3.922868 0.011952 0.498792 C 3.890449 1.155751 0.291192 C 4.278556 2.372411 0.286881 C 3.573401 1.119818 1.770001 C 4.583664 2.070497 0.720117 C 4.495336 0.017203 1.789769 C 4.760496 2.444643 1.597363 C 4.881258 1.2 52579 2.320431 C 4.772880 1.248219 2.572130 C 5.194580 3.763522 2.195079 H 0.195627 3.639667 0.235598 H 4.068215 4.208904 0.777245 H 3.979105 3.411137 2.359049 H 1.028403 1.984463 3.075848 H 1.973882 3.357102 3.678101 H 0.292290 3.341312 4.721522 H 0.794878 5.549130 4.288310 H 0.956972 5.683290 4.113323 H 0.204028 6.814559 2.206358 H 1.563894 5.470411 0.596071 H 2.275903 5.430660 2.218993 H 1.023075 5.648856 0.357709 H 2.020143 5.731866 1.812402 H 2.094333 3.441323 0.802906 H 1.489607 2.156950 2.866334 H 2.317041 3.663214 3.273050 H 4.226593 3.281209 0.308609 H 3.1 86442 2.084688 2.110502 H 4.491145 0.930633 2.344045 H 2.858222 0.340057 2.038875 H 5.074762 1.476174 1.500165 H 5.343730 2.364140 0.009414 H 5.302761 1.279275 3.323720 H 4.035070 2.031795 2.388325 H 5.760117 1.649558 2.303989 H 4.799151 1.044021 3.647616 H 4.883606 4.604652 1.568828 H 4.777141 3.904607 3.199381 H 6.286785 3.809961 2.293994 N 2.425120 2.010881 1.349495 O 3.62207 9 1.883554 1.598004 C 0.788679 5.093361 0.483556 H 0.237971 5.868510 1.016647 C 1.882164 5.530960 0.449199 H 2.107995 4.739002 1.166791 H 1.601638 6.427505 1.010690 O 3.146684 5.746879 0.230 423 C 3.486298 6.931678 0.814679 O 4.530178 6.992152 1.417085 C 2.549690 8.114797 0.649737 H 2.472106 8.412915 0.402265 H 1.539491 7.894307 1.009015 H 2.961044 8.946819 1.221610 C 0.012459 2.545446 2.865340 C 0.582074 3.301514 1.617027 C 1.067912 0.868077 1.404164 C 0.707487 1.166883 2.888170 H 0.192940 3.111135 3.784214 H 1.641175 1.218269 3.457517 C 1.541821 2.279125 0.938102 H 1.592135 2.392171 0.149921 C 0.486953 3.806850 0.689119 C 0.167848 0.294683 0.727484 H 1.196339 4.148492 1.935251 H 1.893509 0.161655 1.319379 H 1.069598 3.053536 0.156419 H 1.079281 0.842 518 0.977067 H 0.087684 0.385576 3.340311 H 1.072832 2.433892 2.777842 O 2.832147 2.577894 1.489518 C 3.983983 2.262524 0.815029 C 4.091419 1.263523 0.156910 C 5.112975 3.009637 1.185932 C 5.327949 1.026303 0.760777 H 3.255773 0.625329 0.416653 C 6.336574 2.767121 0.577629 H 5.005616 3.773533 1.949506 C 6.449885 1.775263 0.405836 H 5.404676 0.226793 1.489290 H 7.208812 3.344586 0.867651 C 7.764478 1.565044 1.097433 F 7.957482 2.461268 2.099116 F 8.810568 1.715567 0.248736 F 7.864750 0.337411 1.649791 C 0.471342 0.623831 1.489422 C 0.312315 0.585143 2.213086 H 0.375395 1.299030 1.437322 H 1.451726 1.086373 1.421929 H 0.687907 0.781676 2.588175 C 1.412342 1.137941 3.090288 H 2.342258 0.600394 2.915685 H 1.140333 1.012222 4.144401 O 1.729830 2.517337 2.822098 C 1.121265 3.586197 3.422252 O 1.424308 4.687669 3.029777

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250 C 0.127005 3.331755 4.533772 H 0.541450 2.698715 5.325531 H 0.770778 2.854206 4.128591 H 0.151706 4.297763 4.955704 TS30E* B3 LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8091323500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8503463700 a.u Ru 0.599610 1.497079 0.241703 O 1.525160 1.445969 0.685242 O 1.507707 2.886751 2.367082 N 2. 744167 2.892738 1.108571 N 3.717265 1.008155 0.580425 C 2.546025 1.714594 0.460980 C 3.989920 2.953243 1.877760 C 1.602394 3.786037 1.332993 C 0.854500 3.394254 2.635988 C 0.399074 4.273428 2.813686 C 0.032811 5.752331 2.891037 C 0.770957 6.142826 1.594014 C 2.034173 5.264789 1.439285 C 0.168312 5.926627 0.389672 C 0.592779 4.437625 0.305133 C 0.678473 3.583434 0.112296 C 1.3322 96 4.060206 1.605270 C 4.079883 0.261952 0.017436 C 3.864252 1.436533 0.766320 C 4.187744 2.671949 0.193572 C 3.413760 1.395622 2.209617 C 4.765857 1.763865 1.301307 C 4.781334 0.320860 1.20 7101 C 4.780341 2.766516 1.069687 C 5.095754 1.578007 1.737502 C 5.282366 0.918811 1.917275 C 5.119609 4.115168 1.661094 H 1.214170 3.964557 0.769736 H 4.505263 3.905897 1.731294 H 3.788267 2.836017 2.951463 H 0.565270 2.333000 2.583531 H 1.521284 3.501033 3.504173 H 0.912063 3.988616 3.741924 H 0.682646 5.913902 3.763289 H 0.848576 6.392815 3.026617 H 1.076169 7.196069 1.646340 H 2.593369 5.549026 0.537758 H 2.698168 5.421587 2.302864 H 0.330744 6.227464 0.541275 H 1.056992 6.564592 0.495104 H 1.250237 4.308724 0.556117 H 1.666369 3.016152 1.558350 H 2.234772 4.67 6205 1.716735 H 3.992433 3.585505 0.748522 H 2.897436 2.319303 2.486463 H 4.287845 1.314835 2.871137 H 2.763988 0.547326 2.435121 H 5.228573 1.136695 2.068736 H 5.550684 2.081939 0.604123 H 5.618355 1.625291 2.691665 H 4.732824 1.818212 1.633030 H 6.340177 1.088564 1.675904 H 5.218778 0.811235 3.005010 H 4.604315 4.916519 1.124937 H 4.843421 4.167419 2.720682 H 6.198586 4.309926 1.600935 N 2.156278 2.147077 1.614848 O 3.377932 2.005651 1.677323 C 0.761010 5.233380 1.131675 H 1.737848 5.578648 1.473070 C 0.025276 6.253950 0.349847 H 0.333066 6.312106 0.684531 H 0.09 9552 7.252818 0.782680 O 1.419801 5.927661 0.224476 C 2.313120 6.249011 1.195586 O 3.457798 5.870960 1.071982 C 1.846838 7.080192 2.374506 H 1.543858 8.083684 2.054074 H 0.993706 6.614629 2.878057 H 2.680824 7.170458 3.070565 C 0.376850 2.158755 3.200808 C 1.196430 2.982402 2.158257 C 1.069540 0.601806 1.447475 C 0.736821 0.675599 2.953823 H 0.594705 2.472057 4.226457 H 1.6292 71 0.404738 3.526590 C 1.895250 1.907214 1.259720 H 1.991656 2.214232 0.213675 C 0.369877 3.981652 1.390952 C 0.214051 0.586295 0.601942 H 2.010030 3.519860 2.653180 H 1.699461 0.254804 1.20 0768 H 0.602449 3.649080 1.027298 H 1.115825 0.819390 1.158723 H 0.066530 0.008996 3.249989 H 0.695414 2.322571 3.045537 O 3.203869 1.765447 1.836237 C 4.291499 1.457522 1.059091 C 4.243156 0.650145 0.080524 C 5.515781 1.978147 1.503965 C 5.421179 0.381050 0.778282 H 3.325802 0.173255 0.402805 C 6.682822 1.705364 0.802243 H 5.528061 2.591933 2.399132 C 6.639957 0.909374 0.349052 H 5.376424 0.274300 1.640897 H 7.629831 2.106827 1.148188 C 7.891841 0.665889 1.139771 F 8.085440 1.617169 2.088911 F 8.996830 0.680033 0.355121

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251 F 7.867476 0.521099 1.782880 C 0.293444 0.84 5353 0.770164 C 0.898319 1.130090 2.036558 C 2.160107 1.027521 2.835236 H 2.757293 1.925539 2.652922 H 2.763028 0.169591 2.526394 O 1.940097 1.033560 4.255182 C 1.755152 0.103353 4.988868 O 1.627935 0.001022 6.183206 C 1.719626 1.436462 4.263371 H 2.654947 1.640278 3.729774 H 0.906011 1.466628 3.531337 H 1.557772 2.215101 5.009020 H 1.198719 1.287516 1.171532 H 0.607628 0.945355 1.367525 H 0.005379 1.127397 2.655322 TS31E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8259072700 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8586017500 a.u Ru 2.217230 0.044792 0.575741 O 2.129339 0.487643 2.720455 O 2.661249 2.062916 1.326879 N 4.043624 0.269338 1.671281 N 2.056782 0.066761 2.592300 C 2.718059 0.136950 1.384672 C 4.358580 0.123838 3.095370 C 5.035179 0.011052 0.615272 C 5.447229 1.485550 0.608924 C 6.433732 1.756874 0.546015 C 7.683944 0.871728 0.377738 C 7.260725 0.611064 0.394159 C 6.306904 0.872704 0.794658 C 6.554738 0.925290 1.732442 C 5.283642 0.04 2256 1.883183 C 4.347762 0.399168 0.703663 C 5.739861 1.433435 1.882538 C 0.749892 0.458201 2.869752 C 0.525633 1.850008 2.751277 C 0.732943 2.354506 3.089197 C 1.619673 2.790741 2.299258 C 2.974153 0.247385 3.740633 C 0.247369 0.380875 3.398515 C 1.765389 1.533623 3.564452 C 1.494320 0.172816 3.720060 C 0.007604 1.843427 3.681670 C 3.115582 2.112466 3.919856 H 4.305202 1.496873 0.696495 H 5.049307 0.902464 3.430404 H 4.822162 0.851542 3.294527 H 4.553499 2.108043 0.491008 H 5.919681 1.752716 1.565151 H 6.724495 2.815568 0.525504 H 8.199863 1.108722 0.564151 H 8.39 5981 1.068964 1.190423 H 8.146754 1.250658 0.285658 H 6.025673 1.933665 0.839471 H 6.823588 0.630667 1.735885 H 6.284916 1.989337 1.777945 H 7.247272 0.736342 2.564923 H 4.789770 0.278509 2. 832813 H 4.900921 2.114638 2.033816 H 6.439898 1.597651 2.713820 H 0.907709 3.424653 2.996594 H 1.289465 3.830387 2.383442 H 2.523116 2.678574 2.911235 H 1.917110 2.614703 1.259596 H 2.785374 0.513811 4.502844 H 2.819625 1.232760 4.197826 H 2.268722 0.481017 4.115734 H 0.778880 2.258733 3.027541 H 0.350241 1.988046 4.715377 H 0.906309 2.434117 3.563953 H 3.673089 2.442600 3.03427 1 H 3.737815 1.379462 4.442436 H 3.010924 2.988836 4.570333 N 2.463678 1.719328 2.552543 O 2.588643 2.499312 3.479363 C 5.314058 2.932962 2.083053 H 5.336542 2.916675 3.173017 C 6.656636 3.093580 1.417749 H 7.319252 2.266220 1.697056 H 7.152268 4.017715 1.741524 O 6.572604 3.025360 0.011354 C 6.242144 4.109878 0.769214 O 5.938428 3.929366 1.925177 C 6.305880 5.482382 0.127388 H 7.318952 5.708024 0.224391 H 5.627354 5.551714 0.729159 H 6.017404 6.217925 0.878467 C 1.757771 3.605760 1.536672 C 2.801783 2.571456 2.009981 C 0.616147 1.411561 1.673738 C 0.390644 2.94 5942 1.807286 H 1.876990 4.573159 2.035150 H 0.049089 3.183354 2.819331 C 2.167705 1.242291 1.542013 H 2.428198 1.071843 0.491305 C 4.163540 2.785071 1.422246 C 0.062786 0.758588 0.479283 H 2.846809 2.558255 3.106766 H 0.321187 0.900935 2.594398 H 4.188508 2.794129 0.331725 H 0.085343 1.373334 0.415285 H 0.383852 3.306803 1.125779 H 1.890248 3.782104 0.459625 O 2.602676 0.117012 2.318989 C 3.274450 0.920117 1.736495

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252 C 2.989364 2.200175 2.237576 C 4.222754 0.768849 0.714744 C 3.615086 3.319724 1.701335 H 2.265226 2.297122 3.040441 C 4.845972 1.896425 0.181609 H 4.49 5862 0.216885 0.355647 C 4.542319 3.172772 0.661888 H 3.361119 4.307133 2.072022 H 5.583957 1.776913 0.604922 C 5.155174 4.387482 0.030930 F 4.356755 4.910169 0.943677 F 6.340560 4.114973 0. 559463 F 5.361061 5.377148 0.924449 C 0.053664 0.630143 0.262309 C 1.665234 1.829048 0.813902 C 1.639307 3.091518 0.003697 H 2.686283 3.404968 0.121293 H 1.221400 2.952070 0.995906 O 1.004028 4.167725 0.720053 C 0.254424 4.627365 0.459728 O 0.775789 5.350147 1.274592 C 0.909044 4.247796 0.854048 H 0.297426 4.569372 1.704758 H 1.057091 3.166935 0.935851 H 1.882746 4.734084 0.899891 H 0.134892 0.996622 0.753413 H 0.567651 1.223322 1.015722 H 1.439405 2.053261 1.869043 TS32E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8104198500 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8526 561900 a.u Ru 0.820529 1.493183 0.090769 O 1.241943 2.206298 0.121497 O 2.292846 1.567015 1.718505 N 3.486891 2.269547 0.723490 N 3.845939 0.354857 0.272739 C 2.864589 1.249203 0.074207 C 4.896 419 2.014989 1.029755 C 2.674514 3.288278 1.395275 C 2.299390 2.822077 2.827380 C 1.348567 3.841369 3.483347 C 2.052742 5.212334 3.554519 C 2.420171 5.677048 2.129715 C 3.390093 4.653200 1.4 92280 C 1.131531 5.789780 1.286497 C 0.429323 4.410560 1.204260 C 1.405588 3.424148 0.531989 C 0.068556 3.950316 2.631151 C 3.710370 0.964244 0.822240 C 3.408718 2.033549 0.047947 C 3.265044 3.317928 0.485879 C 3.360257 1.840338 1.548234 C 5.196676 0.810981 0.128468 C 4.030125 1.216140 2.172718 C 3.458894 3.576291 1.848339 C 3.867900 2.517748 2.664584 C 4.651745 0.171045 3.074666 C 3.271480 4.968715 2.404257 H 1.721099 3.864100 0.427517 H 5.518137 2.882594 0.793940 H 5.027108 1.781113 2.095498 H 1.814499 1.835839 2.767167 H 3.206322 2.697988 3.437187 H 1.098651 3.5 01616 4.497413 H 2.955397 5.144797 4.178776 H 1.390646 5.948636 4.028951 H 2.919985 6.653244 2.178076 H 3.691580 4.981722 0.488646 H 4.301996 4.582455 2.104241 H 1.369260 6.152688 0.277156 H 0.458347 6.530371 1.740609 H 0.483976 4.490044 0.609610 H 0.451475 2.985123 2.590188 H 0.627459 4.664948 3.090670 H 3.038036 4.150300 0.174635 H 2.955386 2.730453 2.037927 H 4.372308 1.689110 1.948680 H 2.766909 0.974891 1.855083 H 5.732428 0.009506 0.644757 H 5.779786 1.092208 0.756818 H 4.097608 2.710280 3.711390 H 4.511700 0.844480 2.702276 H 5.732758 0.345854 3.156313 H 4.2 47178 0.218606 4.091270 H 3.118701 5.693798 1.600863 H 2.398035 5.012179 3.067967 H 4.139825 5.280615 2.997013 N 2.246017 2.316452 0.712256 O 3.109747 3.146662 0.456263 C 1.281209 5.339262 1 .465517 H 2.222073 5.515381 1.988439 C 0.725234 6.543396 0.750298 H 1.240425 6.702502 0.204145 H 0.876279 7.451380 1.345114 O 0.657877 6.398271 0.387897 C 1.654267 6.663027 1.272557 O 2.791396 6.393026 0.952336 C 1.303981 7.302661 2.601217 H 0.875084 8.300964 2.457733 H 0.576937 6.699073 3.153813 H 2.222153 7.393213 3.181733 C 0.313316 2.138627 3.051812 C 1.332140 2.934271 2.1834 01 C 1.097488 0.587772 1.337555 C 0.640060 0.651003 2.811950 H 0.374308 2.419083 4.108236 H 1.470283 0.339138 3.454564

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253 C 1.977048 1.872844 1.229364 H 2.085455 2.233347 0.200402 C 0.735935 4.118814 1.471701 C 0.092106 0.600060 0.372463 H 2.154228 3.290233 2.811101 H 1.712866 0.290214 1.143388 H 0.195309 3.953960 0.928562 H 0.966131 1.131360 0.737587 H 0.207039 0.010567 3.027460 H 0.709489 2.362079 2.727636 O 3.278470 1.652035 1.796841 C 4.295924 1.091211 1.076419 C 4.159037 0.492673 0.178196 C 5.556144 1.136262 1.695902 C 5.275565 0.065002 0.804305 H 3.197332 0.403 968 0.663584 C 6.662224 0.592171 1.060655 H 5.639513 1.600411 2.673435 C 6.528894 0.012390 0.197221 H 5.145881 0.566881 1.756534 H 7.633669 0.625178 1.543975 C 7.745334 0.552248 0.889504 F 8.460632 0.433221 1.492380 F 8.592343 1.154905 0.020411 F 7.437392 1.450868 1.847225 C 0.017075 0.561215 1.030810 C 0.669235 1.445107 1.944163 C 1.703213 1.277174 3.018922 H 2.599512 1.841342 2.752580 H 1.998981 0.228415 3.126489 O 1.300383 1.837419 4.278364 C 0.536197 1.159324 5.188332 O 0.290422 1.698112 6.237930 C 0.045519 0.229531 4.825286 H 0.875358 0.919192 4.632691 H 0.585 337 0.202426 3.931032 H 0.540159 0.604794 5.664629 H 0.733659 1.075594 1.621597 H 0.980265 0.382803 1.497503 H 0.324066 1.726494 2.314215 13E* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8359701600 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8769177400 a.u Ru 0.194674 1.424805 0.403168 O 1.820256 0.874678 0.933633 O 1.378204 2.026674 2.750501 N 1.800880 3.427810 0.881862 N 3.271336 1.842123 0.5 58424 C 1.974536 2.205661 0.315164 C 2.923337 3.867609 1.714754 C 0.465305 4.024567 0.940508 C 0.245329 3.664429 2.272664 C 1.680352 4.225691 2.277060 C 1.624497 5.759603 2.124411 C 0.923197 6.120664 0.798517 C 0.518642 5.566344 0.812880 C 1.706695 5.503497 0.376573 C 1.759754 3.959366 0.227797 C 0.310651 3.437897 0.257677 C 2.460724 3.608488 1.100244 C 4.085709 0.864133 0.111583 C 4.475182 0.298867 0.579411 C 5.362407 1.184839 0.044839 C 4.014014 0.583541 1.989955 C 4.024493 2.897376 1.279144 C 4.623033 1.168316 1.380058 C 5.909123 0.912823 1.302781 C 5.526146 0.2 66486 1.952750 C 4.255201 2.436683 2.117463 C 6.910690 1.855884 1.928950 H 0.176890 3.769897 1.191480 H 3.178792 4.913526 1.525585 H 2.676789 3.762532 2.779828 H 0.263523 2.573035 2.388197 H 0.323353 4.072942 3.120199 H 2.165724 3.965771 3.226879 H 1.087339 6.206737 2.973022 H 2.640665 6.175109 2.134680 H 0.881804 7.211900 0.687078 H 1.047841 5.840000 0.109575 H 1.073362 6.006199 1.654674 H 1.237333 5.771734 1.332450 H 2.727969 5.907711 0.398362 H 2.323112 3.553682 1.068612 H 2.530981 2.520171 1.212323 H 3.488962 3.994048 1.088990 H 5.619803 2.107139 0.468332 H 4.1 83498 1.633214 2.242345 H 4.575918 0.022893 2.714278 H 2.956838 0.347480 2.135783 H 4.578005 2.465815 2.117451 H 4.746836 3.368367 0.601878 H 5.940667 0.494173 2.932802 H 3.175072 2.612119 2 .119937 H 4.723379 3.320797 1.664797 H 4.594120 2.389883 3.156534 H 6.721814 2.892320 1.631391 H 6.887757 1.802687 3.022523 H 7.932761 1.608525 1.612484 N 2.193957 1.329808 2.113464 O 3.319193 1.046914 2.511494 C 0.584054 4.796821 1.392449 H 0.284472 5.436681 1.554361 C 1.737692 5.472388 0.697361 H 1.525881 5.596943 0.370914 H 1.903881 6.476260 1.104075 O 2.951505 4.702009 0.7341 82

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254 C 3.803884 4.768931 1.791212 O 4.756022 4.020156 1.811448 C 3.537715 5.788456 2.880908 H 3.623085 6.810483 2.494229 H 2.534668 5.669445 3.302546 H 4.283947 5.644544 3.662341 C 0.214143 1.785085 3.502310 C 0.625091 2.842367 2.428530 C 1.120737 0.562734 1.578989 C 0.936200 0.472262 3.113010 H 0.475594 2.112039 4.513309 H 1.919922 0.428857 3.590260 C 1.533754 2.052367 1.433663 H 1.491259 2.441574 0.412333 C 0.552628 3.514547 1.767879 C 0.186321 0.131431 0.866477 H 1.264078 3.614756 2.866204 H 1.948568 0.060414 1.233445 H 1.430943 2.897883 1.581657 H 1.016001 0.13 6318 1.575983 H 0.379199 0.419713 3.420952 H 0.873789 1.645291 3.491785 O 2.864136 2.252688 1.943252 C 3.966131 2.104886 1.144205 C 3.980103 1.454992 0.093536 C 5.151497 2.649865 1.665129 C 5.178204 1.358958 0.805033 H 3.099499 0.971595 0.496516 C 6.335543 2.550603 0.949276 H 5.117287 3.144318 2.630833 C 6.355409 1.905524 0.295159 H 5.178943 0.825752 1.749174 H 7.250566 2.968975 1.357175 C 7.634816 1.850180 1.075932 F 7.888886 3.018619 1.718588 F 8.703672 1.622533 0.272254 F 7.623692 0.882163 2.016244 C 0.673912 0.854881 0.477452 C 0.624420 0.012121 1.782063 C 1.79 2792 0.059265 2.743316 H 1.894030 0.888904 3.276820 H 2.736490 0.289128 2.251366 O 1.491200 1.016383 3.786661 C 1.935125 2.302940 3.802800 O 1.502871 3.045825 4.651912 C 2.974548 2.738758 2. 786501 H 3.860369 2.097338 2.810427 H 2.588149 2.720208 1.762506 H 3.263311 3.761172 3.032442 H 1.695132 1.201937 0.316069 H 0.002027 1.697849 0.648597 H 0.282566 0.185187 2.352352 B3LYP/SD D/6 31G(d) SCF energy in gas p hase: 2908.8394365300 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8800394500 a.u Ru 2.231630 0.412835 0.470238 O 2.118674 1.096764 2.518560 O 2.707045 0.998761 2.640372 N 3.939598 0.409274 1.727479 N 1.937324 0.718865 2.550314 C 2.615337 0.300830 1.433617 C 4.232839 0.993632 3.039183 C 4.950584 0.288909 0.677258 C 5.405215 1.689984 0.184701 C 6.429274 1.544996 0.9593 44 C 7.648525 0.739624 0.467446 C 7.185443 0.657165 0.005988 C 6.193742 0.497397 1.166691 C 6.497852 1.388424 1.178031 C 5.264540 0.572916 1.663161 C 4.295575 0.476739 0.474102 C 5.756408 0 .812881 2.133420 C 0.534111 0.961292 2.741803 C 0.020008 2.177681 2.286391 C 1.380695 2.420413 2.507169 C 0.838580 3.229879 1.619753 C 2.834372 1.116391 3.658309 C 0.236119 0.073269 3.518824 C 2.193201 1.512015 3.196939 C 1.594291 0.355682 3.706103 C 0.371999 1.110236 4.238629 C 3.660259 1.790793 3.430367 H 4.080487 1.518943 0.124934 H 4.893650 0.343516 3.621154 H 4.726695 1.966687 2.931147 H 4.526761 2.248608 0.162329 H 5.850985 2.252372 1.016907 H 6.750162 2.545104 1.278729 H 8.149292 1.264127 0.359075 H 8.384441 0.643801 1.276672 H 8.049790 1.240729 0.336708 H 5.878144 1.479068 1.545114 H 6.684338 0.031711 1.996588 H 6.190337 2.396809 0.869199 H 7.205725 1.511807 2.008938 H 4.787585 1.106751 2.490841 H 4.919171 1.397559 2.520865 H 6.473829 0.68 2391 2.955171 H 1.817933 3.351255 2.152392 H 0.227231 4.079461 1.301814 H 1.599065 3.616210 2.311200 H 1.370623 2.846003 0.743809 H 2.599952 2.133953 3.987424 H 2.696960 0.447522 4.515293 H 2.195435 0.340767 4.288171 H 1.314550 1.432923 3.793499 H 0.573022 0.851540 5.287285

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255 H 0.313398 1.964343 4.253637 H 4.003543 2.672395 2.881465 H 4.275896 0.935206 3.126611 H 3.859680 1.961910 4.496267 N 2.436374 0.069239 3.255602 O 2.452885 0.171859 4.473704 C 4.712514 3.204654 2.107719 H 4.862512 3.135476 3.185418 C 5.910729 3.672986 1.322351 H 6.723436 2.940110 1.384129 H 6.30 3393 4.615344 1.724642 O 5.634847 3.788460 0.081359 C 5.011746 4.881134 0.600313 O 4.563881 4.808130 1.722857 C 4.939942 6.141052 0.238937 H 5.941591 6.499105 0.502118 H 4.388584 5.964367 1. 168201 H 4.429125 6.906141 0.345874 C 1.085083 3.298580 1.983360 C 2.307121 2.397982 2.262447 C 0.264251 0.966362 1.964940 C 0.132375 2.425605 2.329369 H 1.124625 4.234761 2.550519 H 0.349363 2.486355 3.400501 C 1.822938 1.010173 1.771453 H 2.062756 0.899773 0.707914 C 3.543643 2.867724 1.557053 C 0.388101 0.440755 0.688341 H 2.477128 2.326867 3.344474 H 0.067831 0.289552 2.79973 3 H 3.444748 2.939237 0.473072 H 0.151531 1.108403 0.136608 H 1.039901 2.745761 1.813313 H 1.073487 3.570247 0.918245 O 2.436128 0.064639 2.500486 C 3.289181 0.936695 1.891904 C 3.326785 2.232451 2.432521 C 4.117664 0.613697 0.807181 C 4.153101 3.199748 1.875023 H 2.689897 2.459153 3.281543 C 4.938380 1.593656 0.250116 H 4.147257 0.396006 0.414858 C 4.956035 2.889396 0.770306 H 4.169439 4.201543 2.291784 H 5.579782 1.340675 0.588047 C 5.771271 3.959929 0.108623 F 5.057371 4.626083 0.839438 F 6.859925 3.457885 0.517934 F 6.199855 4.890453 0.988813 C 0.019645 1.043 914 0.316540 C 1.173781 2.042843 0.029388 C 1.133885 2.833157 1.270424 H 2.117419 2.843292 1.748679 H 0.417241 2.414001 1.978643 O 0.866283 4.231720 1.033083 C 0.385940 4.771065 0.987540 O 0.493293 5.935705 0.688611 C 1.573057 3.895260 1.343495 H 1.497149 3.522583 2.371802 H 1.653450 3.029202 0.680645 H 2.479855 4.492312 1.248941 H 0.628912 0.988060 0.588432 H 0.593121 1.444471 1.154740 H 1.317756 2.736966 0.865218 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2908.8297904800 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2907.8726487200 a.u Ru 0.725950 1.544549 0.201465 O 1.381535 2.170950 0.010719 O 2.588525 1.788134 1.790651 N 3.391451 2.435599 0.457457 N 3.765717 0.402402 0.252738 C 2.780149 1.329725 0.053388 C 4.802870 2.237291 0.799269 C 2.586991 3.531555 0.998524 C 2.3 44891 3.335261 2.520526 C 1.411743 4.437688 3.057047 C 2.059848 5.815336 2.809522 C 2.292084 6.013067 1.297021 C 3.245885 4.913217 0.775726 C 0.939877 5.926019 0.559246 C 0.286087 4.540432 0 .802660 C 1.245909 3.473452 0.255208 C 0.062953 4.350407 2.316234 C 3.709119 0.898274 0.860855 C 3.518984 2.031281 0.043032 C 3.490931 3.296482 0.640295 C 3.462586 1.924879 1.464783 C 5.111477 0.917985 0.085491 C 4.017621 1.046913 2.228611 C 3.702708 3.464961 2.013455 C 3.985094 2.332800 2.783457 C 4.446968 0.116374 3.096197 C 3.687029 4.845231 2.628668 H 1.427189 3.662752 0.8298 16 H 5.420476 3.066394 0.443577 H 4.930053 2.158595 1.887165 H 1.899789 2.344327 2.686352 H 3.304380 3.357824 3.056185 H 1.261375 4.287584 4.134322 H 3.011831 5.891477 3.354191 H 1.407758 6 .610299 3.194276 H 2.752967 6.993196 1.118715 H 3.450616 5.054013 0.294049 H 4.207274 4.974995 1.306206 H 1.081090 6.093924 0.517292 H 0.267350 6.717347 0.917224

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256 H 0.670727 4.487147 0.282152 H 0.418879 3.382834 2.502718 H 0.621577 5.124341 2.687921 H 3.333689 4.171075 0.013667 H 3.059610 2.842189 1.902194 H 4.475502 1.799530 1.872976 H 2.873677 1.073372 1.813621 H 5.646417 0.200572 0.714138 H 5.695977 1.069777 0.829647 H 4.203111 2.448399 3.843914 H 4.095877 1.077247 2.713720 H 5.542683 0.163647 3.156499 H 4.078014 0.005022 4.120708 H 3.074043 5.532976 2.038315 H 3.298103 4.825800 3.652560 H 4.699842 5.267059 2.673642 N 2.216795 2.592671 0.914505 O 2.616753 3.754187 0.848661 C 0.945496 5.038328 1.955850 H 1.879414 5.240433 2.481486 C 0.303837 6.242 139 1.314249 H 0.773271 6.473665 0.351338 H 0.423758 7.129738 1.945961 O 1.081880 6.031881 0.992168 C 2.048255 6.137290 1.942370 O 3.164003 5.751372 1.669918 C 1.694959 6.757815 3.278770 H 1.352891 7.791810 3.157030 H 0.899082 6.195169 3.777159 H 2.590865 6.750245 3.899648 C 0.139109 1.703313 3.351060 C 1.122404 2.599029 2.542600 C 1.031279 0.291810 1.563857 C 0.553782 0.253448 3.034054 H 0.173563 1.928458 4.421982 H 1.394783 0.043251 3.670743 C 1.824562 1.631981 1.528332 H 1.910254 2.063628 0.524796 C 0.468304 3.790774 1.898885 C 0.161948 0.225517 0.597267 H 1.922 603 2.956733 3.197248 H 1.709352 0.531179 1.342447 H 0.457997 3.608336 1.353133 H 0.995212 0.836431 0.945120 H 0.254778 0.467476 3.199890 H 0.891631 1.887323 3.026224 O 3.147181 1.464654 2.0 71290 C 4.196104 1.044679 1.301649 C 4.085025 0.402382 0.064732 C 5.466594 1.282420 1.852660 C 5.239257 0.009192 0.615788 H 3.126255 0.148651 0.365786 C 6.607745 0.893084 1.167127 H 5.530516 1.774093 2.818193 C 6.501233 0.256111 0.076935 H 5.135143 0.518118 1.557736 H 7.586824 1.077003 1.598421 C 7.745892 0.106112 0.831944 F 8.259816 0.959635 1.498365 F 8.726954 0.542695 0.004593 F 7.529124 1.071492 1.749300 C 0.076650 0.502228 0.953958 C 0.230913 0.700818 1.940786 C 1.169743 0.477073 3.112109 H 1.864275 1.315272 3.194746 H 1.754193 0.437398 3.004732 O 0.477683 0.502298 4.378267 C 0.035806 0.604568 4.984634 O 0.555268 0.476361 6.066211 C 0.073781 1.943091 4.276044 H 1.113685 2.214889 4.063978 H 0.466419 1.930228 3.324200 H 0.368153 2.698054 4.926743 H 0.550003 1.350742 1.235300 H 1.136921 0.726490 1.085347 H 0.700665 1.154295 2.288883 TS8 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.12625898000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.14916849000 a.u Ru 1.671455 0.163570 0.330898 O 1.657494 1.642992 1.774589 O 1.244716 0.361762 2.490855 N 3.700394 0.677812 1.551900 N 1.865894 0.602897 2.744050 C 2.376156 0.379897 1.491457 C 4.099223 1.320656 2.806966 C 4.510665 0.696276 0.329406 C 4.632543 2.133283 0.240450 C 5.441834 2.113231 1.554042 C 6.846130 1.533780 1.293885 C 6.708476 0.098528 0.747475 C 5.935509 0.148729 0.590236 C 5.953036 0.770574 1.778849 C 4.530379 0.192192 2.019862 C 3.792664 0.248447 0.658316 C 4.700690 1.237377 2.581902 C 0.563196 0.274448 3.245569 C 0.417591 1.284086 3.320169 C 1.686692 0.949 195 3.800643 C 0.121386 2.717893 2.940375 C 2.910068 0.988183 3.714866 C 0.301921 1.019405 3.741310 C 1.999739 0.344588 4.229161 C 0.985218 1.306170 4.210375 C 1.369485 2.088707 3.830053 C 3.397556 0.695984 4.680144 H 3.970627 1.262308 0.274975

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257 H 5.043816 0.918895 3.182805 H 4.219140 2.403713 2.666275 H 3.632779 2.542378 0.422880 H 5.131533 2.783006 0.493538 H 5.529411 3.138804 1.936082 H 7.394554 2.161106 0.576393 H 7.428220 1.528957 2.225267 H 7.704658 0.326829 0.566671 H 5.865021 0.852563 1.036539 H 6.483287 0.786841 1.300003 H 5.886281 1.807759 1.421932 H 6.518118 0.794005 2.721593 H 4.005806 0.815927 2.753632 H 3.740971 1.693876 2.827338 H 5.279480 1.191089 3.515192 H 2.453953 1.719868 3.833890 H 0.196811 3.294195 3.820291 H 0.677667 2.795511 2.198941 H 1.014768 3.210109 2.542713 H 2.579508 1.835513 4.322456 H 3.126772 0.148199 4.388350 H 1.198453 2.311047 4.569219 H 1.769817 2.148407 4.851279 H 0.957432 3.075337 3.592825 H 2.20 9882 1.901067 3.158147 H 4.019309 0.989043 3.824361 H 3.393680 1.534463 5.384278 H 3.888737 0.155068 5.163993 C 1.326634 1.935013 0.172960 H 1.208069 2.335544 1.185015 C 1.212533 3.027439 0. 848365 H 0.922446 2.644966 1.830852 H 2.216224 3.477318 0.945901 N 1.387815 0.889692 2.776859 O 1.271798 1.314126 3.912495 O 0.281148 4.022238 0.377064 C 0.458246 0.723069 0.071336 H 0.226665 1.603559 0.513488 C 1.389473 0.623340 1.294612 H 0.977777 0.829697 2.287963 C 1.576631 0.897504 0.896626 H 1.172174 1.604406 1.634455 C 0.701495 0.591847 0.317227 H 0.742441 1.067717 1.28788 5 O 2.600198 1.335068 1.124488 O 2.856303 1.280702 0.480152 C 2.486945 2.709484 1.492281 C 3.740391 1.591279 1.559104 C 3.821348 3.390281 1.304383 C 4.978879 2.857170 1.888620 C 3.921367 4. 573963 0.566233 C 6.209125 3.494748 1.733285 H 4.912384 1.934581 2.458003 C 5.150716 5.220819 0.417155 H 3.030242 4.994558 0.105116 C 6.298029 4.680981 0.999038 H 7.099058 3.067611 2.187989 H 5.211157 6.141242 0.157796 H 7.256576 5.179565 0.881541 C 5.135558 1.763020 1.012148 C 5.846201 2.951339 1.204284 C 5.740410 0.711338 0.308427 C 7.146681 3.089430 0.711713 H 5.379034 3.776096 1.737693 C 7.035340 0.850035 0.188652 H 5.184260 0.208704 0.153788 C 7.743301 2.039051 0.013940 H 7.687938 4.018989 0.867771 H 7.495489 0.028640 0.732222 H 8.753818 2.145232 0.372416 C 0.045259 5.113437 1.128886 O 0.811132 5.923566 0.667120 C 0.573344 5.234996 2.509031 H 1.667901 5.221472 2.465047 H 0.263136 4.406931 3.156607 H 0.240742 6.176193 2.947125 H 3.404285 2.510 761 2.064042 H 3.717264 0.774306 2.294099 H 1.717827 3.211373 0.886539 H 2.161240 2.776523 2.544187 TS9 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.15074207000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2 493.18237060000 a.u Ru 1.738739 0.177999 0.301108 O 2.236575 1.584818 3.725756 O 1.315185 0.092066 2.421758 N 3.498548 0.170759 1.979471 N 1.526048 0.598541 2.835593 C 2.191030 0.365998 1.665619 C 3.741630 0.071991 3.422238 C 4.392378 0.375756 0.956211 C 4.427698 1.926860 1.033577 C 5.300440 2.493701 0.102422 C 6.733225 1.938541 0.034358 C 6.700458 0.398107 0.046888 C 5.834510 0.1614 53 1.103534 C 6.096499 0.024981 1.400084 C 4.653675 0.529742 1.539134 C 3.801609 0.056190 0.401567 C 4.695016 2.069592 1.454213 C 0.174064 1.053538 3.010291 C 0.832873 0.128427 3.347300 C 2 .144120 0.598059 3.497087 C 0.556465 1.342016 3.571685 C 2.443613 0.658092 3.993464 C 0.113066 2.433863 2.923294 C 2.473879 1.946341 3.342695

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258 C 1.437649 2.849751 3.077065 C 0.970616 3.468961 2.708521 C 3.906371 2.415502 3.436105 H 3.835192 1.172113 0.465157 H 4.629395 0.635813 3.720711 H 3.883877 0.975723 3.720022 H 3.402013 2.311200 0.956343 H 4.827420 2.241439 2.008052 H 5.3196 23 3.588812 0.027460 H 7.176232 2.260141 0.987806 H 7.369306 2.340843 0.765034 H 7.719074 0.000095 0.049188 H 5.821774 1.259599 1.078857 H 6.261755 0.140369 2.071160 H 6.088360 1.120136 1.488904 H 6.716304 0.356108 2.222999 H 4.266556 0.215357 2.508527 H 3.685055 2.478463 1.572842 H 5.296804 2.468766 2.281076 H 2.929468 0.117288 3.732383 H 0.759620 1.614372 4.615333 H 0.4797 14 1.606728 3.350715 H 1.205316 1.965683 2.946192 H 2.041430 0.083465 4.832506 H 2.570111 1.698360 4.319403 H 1.667970 3.908848 2.983046 H 1.410671 3.779826 3.665985 H 0.559947 4.368364 2.23 9293 H 1.786006 3.100113 2.080127 H 4.373832 2.438400 2.442960 H 3.970781 3.427038 3.851214 H 4.506480 1.748822 4.063893 C 0.372600 1.709712 0.446787 H 0.363119 2.379943 0.409601 C 0.326926 2.523447 1.724599 H 0.294015 1.902282 2.617068 H 1.210218 3.170214 1.781553 N 2.109175 0.395651 3.426997 O 2.648656 0.536679 4.035860 O 0.869176 3.341607 1.618195 C 0.186375 0.961495 0.019087 H 0.015352 1.377829 1.010931 C 0.695862 1.590300 1.065555 H 0.160783 2.021165 1.917414 C 1.353896 0.202962 1.376960 H 1.105072 0.156315 2.380243 C 0.558829 0.528577 0.242362 H 1.167441 0.67 7741 0.650224 O 1.541362 2.537867 0.452834 O 2.742225 0.186925 1.156194 C 2.320615 3.292181 1.380598 C 3.351087 1.016111 1.638905 C 3.350309 4.095855 0.623713 C 3.560811 5.447944 0.911457 C 4.137129 3.479336 0.359764 C 4.546707 6.174287 0.238393 H 2.948613 5.937548 1.665734 C 5.116570 4.204846 1.037367 H 3.968903 2.430863 0.586341 C 5.326303 5.554443 0.738682 H 4.698879 7.224589 0.473340 H 5.720158 3.716653 1.798594 H 6.091104 6.118521 1.266269 C 4.756057 1.162359 1.108032 C 5.579666 0.054310 0.877037 C 5.262042 2.449934 0.883012 C 6.887593 0.231928 0.422105 H 5.192911 0.945723 1.045313 C 6.573638 2.626239 0.436893 H 4.626183 3.312938 1.071928 C 7.389291 1.516879 0.202335 H 7.516736 0.636317 0.242474 H 6.955826 3.630146 0.270237 H 8.409012 1.652714 0.148792 C 1.254436 4.194960 2.605332 O 2.334578 4.731859 2.509406 C 0.295731 4.426562 3.755098 H 0.658413 4.829597 3.397141 H 0.072708 3.494458 4.285634 H 0.752265 5.136544 4.445058 H 3.35 7382 0.987492 2.742612 H 2.757864 1.888295 1.343452 H 2.818962 2.606338 2.079954 H 1.667188 3.955088 1.969232 TS10 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.15867587000 a.u. M06/SDD/6 311++G(d,p) SCF energy i n solution: 2493.18580653000 a.u Ru 1.453346 0.078212 0.393957 O 2.721136 0.902345 2.361294 O 1.084891 0.519334 2.504396 N 3.075267 0.663112 1.922369 N 1.677910 0.863728 2.638697 C 2.060418 0.150011 1.536183 C 3.294004 0.678976 3.370373 C 3.547831 1.691399 0.991506 C 2.771811 3.019353 1.189487 C 3.203158 4.040601 0.119425 C 4.714142 4.313928 0.262181 C 5.495018 2.996303 0.075421 C 5.05 8878 1.980636 1.157419 C 5.200370 2.431856 1.330057 C 3.682700 2.143033 1.474771 C 3.302573 1.096290 0.410697 C 2.902289 3.459178 1.277406 C 0.881771 2.058543 2.691515 C 0.397477 1.990410 3. 282301 C 1.146280 3.165311 3.389058

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259 C 0.963143 0.687522 3.801140 C 2.562463 0.597997 3.796842 C 1.417691 3.288318 2.259570 C 0.653459 4.399937 2.949312 C 0.626709 4.437502 2.392986 C 2.779134 3.406049 1.612564 C 1.472146 5.660257 3.107126 H 3.976297 0.232193 0.519078 H 4.358291 0.662038 3.619492 H 2.848690 1.577774 3.819540 H 1.695969 2.823272 1.117952 H 2.968752 3.420354 2.19428 1 H 2.643235 4.974111 0.264216 H 4.928667 4.747438 1.249508 H 5.037911 5.049099 0.486751 H 6.571167 3.186277 0.181299 H 5.624759 1.044964 1.058197 H 5.273447 2.392119 2.155113 H 5.772922 1.510631 1.500944 H 5.521544 3.154412 2.093557 H 3.495847 1.755415 2.480378 H 1.825805 3.279695 1.389768 H 3.189814 4.182579 2.052852 H 2.138912 3.115584 3.831879 H 0.364816 0.282601 4.626881 H 0.995727 0.086547 3.027337 H 1.981129 0.832281 4.174625 H 1.979461 0.479182 4.713790 H 3.251899 1.441301 3.936460 H 1.029700 5.386743 2.046503 H 3.460331 2.605106 1.910553 H 3.242741 4.363 549 1.870967 H 2.694091 3.374150 0.519078 H 2.540539 5.464589 2.965099 H 1.168204 6.427668 2.388189 H 1.351680 6.086631 4.112042 C 0.269882 1.707791 0.596280 H 0.477352 2.400894 0.212099 C 0.235234 2.481468 1.901685 H 0.733029 2.999678 1.992257 H 0.361260 1.863756 2.788454 N 1.998219 0.180953 3.105144 O 2.108346 0.141565 4.325891 O 1.258991 3.479571 1.788660 C 0.149550 0.970726 0.158765 H 0.422560 1.210988 1.191034 C 1.177911 1.485279 0.856185 H 0.731797 2.023381 1.703559 C 1.655651 0.051200 1.258691 H 1.408700 0.186381 2.301566 C 0.745309 0.707000 0.251942 H 1.242 957 0.913589 0.696569 O 2.124615 2.287248 0.194224 O 3.030206 0.121249 1.014562 C 3.020060 2.973937 1.079335 C 3.540401 1.383256 1.421232 C 3.949961 3.828537 0.256743 C 5.240879 3.383997 0.0 52324 C 3.526062 5.071226 0.231407 C 6.094666 4.168202 0.830759 H 5.575902 2.418278 0.318952 C 4.375018 5.856406 1.011350 H 2.524563 5.423637 0.004977 C 5.663142 5.405837 1.311637 H 7.096637 3.814129 1.059185 H 4.035109 6.820600 1.380393 H 6.328053 6.018859 1.914573 C 5.011138 1.470650 1.081186 C 5.538053 0.779596 0.017092 C 5.858004 2.281654 1.845147 C 6.890374 0.901143 0.342424 H 4.886789 0.137622 0.601175 C 7.208093 2.409739 1.514710 H 5.461550 2.813774 2.707567 C 7.728689 1.718335 0.419121 H 7.289178 0.356024 1.194165 H 7.853809 3.041496 2.118925 H 8.780925 1.8 11702 0.164140 H 2.431016 3.597880 1.770936 H 3.587209 2.246463 1.670553 H 2.987196 2.190920 0.911365 H 3.389405 1.524052 2.504074 C 1.866619 4.061110 2.863668 O 2.702251 4.905599 2.647473 C 1.462848 3.613421 4.252559 H 1.819689 2.595516 4.447319 H 0.376400 3.626050 4.393325 H 1.927536 4.291917 4.968772 TS11 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.18389783000 a.u. M06/SDD/6 311++G(d,p) SCF en ergy in solution: 2493.19852876000 a.u Ru 0.595365 0.983899 1.011903 O 2.077551 0.128425 2.187129 O 0.019824 0.522312 2.596600 N 0.792020 3.507073 0.360349 N 2.617272 2.382126 0.852438 C 1.452313 2.337071 0.159154 C 1.422715 4.343347 1.385630 C 0.599144 3.596038 0.093436 C 1.580662 3.253965 1.056382 C 3.027083 3.225641 0.525335 C 3.383685 4.606219 0.059543 C 2.408654 4.944074 1.206332 C 0.961834 4.989957 0.655687 C 2.532086 3.864387 2.304833 C 2.160733 2.474401 1.720898 C 0.708631 2.555285 1.228276

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260 C 3.128197 2.142408 0.567104 C 3.741902 1.499565 0.691251 C 4.046203 0.590 459 1.723668 C 5.191080 0.200727 1.599064 C 3.155282 0.448655 2.936066 C 2.819896 3.704031 1.486397 C 4.567306 1.616094 0.441483 C 6.042314 0.101523 0.489972 C 5.706662 0.806067 0.516794 C 4.252449 2.562223 1.577921 C 7.294897 0.941655 0.404393 H 0.090230 2.940212 2.079644 H 1.458645 5.394817 1.086524 H 0.873659 4.273895 2.334569 H 1.318263 2.279048 1.479719 H 1.486835 4.002731 1.855912 H 3.707629 2.980446 1.350262 H 3.330592 5.376275 0.723258 H 4.415963 4.603960 0.434748 H 2.657787 5.926928 1.627279 H 0.253897 5.262735 1.449932 H 0.889128 5.760098 0.126476 H 1.875022 4.105174 3.152012 H 3.560382 3.849130 2.692252 H 2.240019 1.713054 2.507092 H 2.889287 1.166103 0.133507 H 4.156775 2.088246 0.949567 H 5.425501 0.916715 2.382985 H 2.985970 1.406607 3.442412 H 2.171064 0.051741 2.661909 H 3.601209 0.237789 3.661641 H 3.170258 3.593921 2.516022 H 3.575253 4.272860 0.928287 H 6.351448 0.894476 1.388719 H 3.842278 3.517222 1.233343 H 5.15 4246 2.774913 2.160441 H 3.517516 2.118496 2.260921 H 8.047700 0.597777 1.126230 H 7.078038 1.990014 0.634263 H 7.745076 0.885323 0.592323 C 1.193124 3.437980 2.174917 H 1.448077 3.564366 3. 225956 C 2.054242 4.223601 1.230417 H 1.790766 5.289016 1.268916 H 1.936335 3.888031 0.199560 N 1.201077 0.805712 2.872884 O 1.524403 1.639834 3.690848 O 3.422681 4.119863 1.674342 C 0.107187 0.094085 0.418654 H 0.146695 0.319273 1.463082 C 1.084673 1.062207 0.311646 H 1.596046 1.048829 0.658597 C 0.330046 2.421168 0.428032 H 0.524661 2.360871 0.262175 C 0.157503 2.662832 1.83783 4 H 0.424742 2.189144 2.623727 O 2.039403 0.862345 1.356743 O 1.132202 3.549595 0.055272 C 3.285453 1.536465 1.195917 C 1.282214 3.794532 1.352407 C 4.309410 0.969426 2.154410 C 3.941942 0. 215564 3.274143 C 5.667632 1.234818 1.932472 C 4.915536 0.265144 4.153731 H 2.892448 0.004158 3.448186 C 6.639165 0.760436 2.813295 H 5.963826 1.814306 1.060140 C 6.265740 0.006255 3.928754 H 4.615596 0.852154 5.018408 H 7.688511 0.973176 2.625207 H 7.021755 0.368107 4.613999 C 2.684460 3.520608 1.856147 C 3.774080 4.208239 1.302128 C 2.915449 2.599491 2.884618 C 5.070299 3.969623 1.757432 H 3.601020 4.927375 0.505167 C 4.213728 2.365409 3.348470 H 2.076531 2.061807 3.319270 C 5.293267 3.045924 2.784080 H 5.906138 4.510006 1.320143 H 4.378604 1.650031 4.150046 H 6.302626 2.863655 3.143631 H 3.640233 1.424261 0.161335 H 3.152532 2.613019 1.368040 H 1.042399 4.856754 1.495562 H 0.554806 3.207933 1.926518 C 4.457957 3.794067 0.860225 O 5.561486 3.71 9368 1.354091 C 4.190310 3.539084 0.610870 H 3.582717 2.638205 0.756167 H 3.673776 4.378554 1.088304 H 5.151583 3.388434 1.102036 TS12 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.18105231000 a.u. M06/SDD /6 311++G(d,p) SCF energy in solution: 2493.19632972000 a.u Ru 0.827676 1.336666 0.939348 O 2.252870 0.410535 2.315014 O 0.140655 0.130520 2.740771 N 1.234940 3.623549 0.760612 N 2.910935 2.247824 1.138503 C 1.773855 2.424024 0.419028 C 1.919714 4.245234 1.898845 C 0.145995 3.887008 0.340437 C 1.145862 3.476854 1.452206 C 2.592127 3.639814 0.946929 C 2.834186 5.111581 0.558349 C 1.841670 5.51 7343 0.550867

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261 C 0.392318 5.368075 0.026425 C 2.065602 4.608378 1.780071 C 1.807516 3.126449 1.394178 C 0.350402 3.020058 0.921268 C 2.791337 2.723385 0.276720 C 3.896633 1.224403 0.922376 C 4.011231 0.183517 1.862326 C 4.996690 0.788391 1.661564 C 3.107746 0.105306 3.070681 C 3.235111 3.444522 1.945211 C 4.769097 1.310210 0.179526 C 5.864170 0.747003 0.565814 C 5.737975 0.314413 0.335434 C 4.675871 2.432042 1.187586 C 6.898786 1.826750 0.349771 H 0.292870 3.461574 1.724973 H 2.082374 5.314958 1.739366 H 1.334397 4.119280 2.819542 H 0.964579 2.436191 1.740267 H 0.987219 4.102613 2.341922 H 3.285469 3.345271 1.744976 H 2.709727 5.760928 1.436585 H 3.865441 5.246376 0.205170 H 2.009424 6.564899 0.833113 H 0.330289 5.683439 0.791148 H 0.247495 6.019091 0.848446 H 1.397837 4.905638 2.600404 H 3.094622 4.730158 2.146093 H 1.956988 2.487443 2.273489 H 2.631066 1.680697 0.018092 H 3.823157 2.805472 0.645663 H 5.087644 1.597977 2.382548 H 3.300 293 0.920374 3.780821 H 2.051347 0.169209 2.790601 H 3.261537 0.835783 3.607038 H 3.532242 3.165685 2.959529 H 4.066856 3.992552 1.483432 H 6.412325 0.372823 1.187150 H 4.551015 3.411368 0.7 12451 H 5.580500 2.471230 1.801904 H 3.825559 2.281889 1.861943 H 7.153385 2.333173 1.286409 H 6.529967 2.591648 0.346137 H 7.820779 1.418639 0.078579 C 0.352994 4.019744 1.472672 H 0.704666 4.255400 2.476843 C 0.148529 5.239005 0.611571 H 0.839734 5.675196 0.787924 H 0.221200 5.017836 0.453352 N 1.349937 0.117248 3.093228 O 1.640514 0.788848 4.057963 O 1.063919 6.287062 0.993024 C 0.044523 0.290033 0.334062 H 0.303182 0.335717 1.400065 C 1.011681 0.765297 0.058848 H 1.563749 0.523679 0.858717 C 0.362204 2.172922 0.147587 H 0.491342 2.021848 0.828976 C 0.138619 2.7 36182 1.162989 H 0.336205 1.995664 1.933322 O 1.887476 0.716645 1.185743 O 1.254424 3.117025 0.743330 C 3.185979 1.294838 0.995495 C 1.413431 3.049047 2.171148 C 3.980837 1.106542 2.264088 C 3.502484 1.624405 3.476370 C 5.206775 0.433345 2.254570 C 4.235746 1.471151 4.651816 H 2.549326 2.146150 3.489777 C 5.948488 0.285106 3.429709 H 5.584743 0.024337 1.320266 C 5.463592 0.802344 4.631119 H 3.853515 1.877451 5.584856 H 6.901176 0.237766 3.405600 H 6.037453 0.686664 5.546927 C 2.784130 2.555982 2.586899 C 3.934822 3.227124 2.148281 C 2.925231 1.445778 3.427745 C 5.201687 2.789909 2.532231 H 3.832777 4.092154 1.497489 C 4.194864 1.011552 3.820748 H 2.038519 0.919087 3.770572 C 5.334710 1.679424 3.371810 H 6.085445 3.317631 2.182945 H 4.290164 0.150106 4.476836 H 6.321908 1.341379 3.676012 H 3.690921 0.811371 0.146732 H 3.084905 2.359347 0.754735 H 1.264900 4.074574 2.535945 H 0.634363 2.420109 2.615360 C 2.352122 6.312209 0.551886 O 3.090 237 7.167960 0.978684 C 2.784422 5.277861 0.472200 H 2.611982 4.257569 0.114375 H 2.232393 5.398636 1.411640 H 3.847036 5.423984 0.667437 TS13 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.15259828000 a .u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.18090482000 a.u Ru 1.689557 0.357974 0.236882 O 1.939628 0.917178 3.315798 O 1.606072 1.015844 2.300510 N 3.405645 0.417095 1.961097 N 1.406287 0.316081 2.855264 C 2.106035 0.135366 1.697854 C 3.626338 0.959164 3.307133 C 4.353758 0.561892 0.852169

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262 C 4.531430 2.057647 0.477956 C 5.472588 2.188995 0.735238 C 6.845252 1.578111 0.386474 C 6.666 810 0.089267 0.024677 C 5.739908 0.030027 1.205575 C 6.045333 0.656163 1.223354 C 4.661124 0.044378 1.568717 C 3.746189 0.195199 0.342199 C 4.850544 1.443644 1.930526 C 0.050546 0.075459 3.1 29521 C 0.972650 0.891543 3.113325 C 2.282202 0.478189 3.393077 C 0.722291 2.349601 2.799290 C 2.287477 0.651635 3.994933 C 0.224355 1.412436 3.493170 C 2.596306 0.848216 3.694772 C 1.547646 1.773989 3.755818 C 0.872113 2.446945 3.628469 C 4.025536 1.278468 3.925743 H 3.718074 1.292769 0.073277 H 4.476280 0.478474 3.799577 H 3.824412 2.037555 3.259260 H 3.548032 2.484401 0.245153 H 4.942905 2.611161 1.333933 H 5.592700 3.252533 0.980118 H 7.304121 2.120155 0.453025 H 7.527779 1.676155 1.241109 H 7.641789 0.351329 0.222025 H 5.623674 1.081215 1.502706 H 6.186300 0.5 03808 2.057671 H 5.939271 1.725450 0.992075 H 6.712529 0.583913 2.093283 H 4.241283 0.585801 2.420508 H 3.886597 1.882617 2.203782 H 5.505499 1.528483 2.808263 H 3.077999 1.219695 3.363705 H 1.178553 2.989074 3.563892 H 0.343596 2.583783 2.750230 H 1.170500 2.627531 1.837638 H 1.884641 1.500329 4.555297 H 2.361061 0.203375 4.678099 H 1.766690 2.808061 4.013307 H 1.401669 2.344729 4.585266 H 0.453572 3.457665 3.601542 H 1.621720 2.368481 2.835029 H 4.489949 1.608137 2.987083 H 4.083762 2.114372 4.631067 H 4.632687 0.456359 4.318859 C 0.069005 1.880698 0.035564 H 0.0 97464 2.240063 1.060449 C 0.131303 3.010060 0.968639 H 0.196560 2.656865 1.995932 H 0.995201 3.652205 0.765943 N 1.941834 0.322401 3.371271 O 2.221199 0.966433 4.382442 O 1.094751 3.765853 0.767467 C 0.531224 1.107154 0.409127 H 0.469613 1.876360 0.367886 C 0.538270 1.301378 1.476159 H 0.100470 1.553064 2.449577 C 1.212004 0.109381 1.468916 H 0.867909 0.682885 2.334608 C 0.6770 02 0.699663 0.158312 H 1.158791 0.265579 0.713883 O 1.390086 2.336306 1.015055 O 2.622311 0.023827 1.441586 C 2.168917 2.959714 2.039680 C 3.287482 1.225664 1.872794 C 3.189610 3.862116 1.39 1461 C 3.292769 5.210103 1.747570 C 4.068572 3.342493 0.429312 C 4.263347 6.028637 1.163553 H 2.609626 5.623738 2.486105 C 5.033103 4.159619 0.158883 H 3.985071 2.296136 0.150200 C 5.134983 5.505148 0.208328 H 4.332748 7.074478 1.451387 H 5.710254 3.746352 0.902346 H 5.889032 6.140499 0.249083 C 4.623596 1.353320 1.181836 C 5.547564 0.299226 1.199470 C 4.957492 2.543232 0.522759 C 6.780593 0.429101 0.560825 H 5.295021 0.628046 1.706449 C 6.197484 2.675845 0.109309 H 4.251553 3.371274 0.514382 C 7.109274 1.619019 0.095257 H 7.488001 0.396137 0.579479 H 6.448345 3.60 7056 0.610760 H 8.072881 1.721854 0.587801 C 1.357725 4.912722 1.451728 O 2.443742 5.426503 1.309338 C 0.270273 5.475340 2.343833 H 0.626819 5.722704 1.764955 H 0.028300 4.754843 3.113279 H 0.651620 6.378644 2.820373 H 2.670907 2.187274 2.635978 H 1.511173 3.534182 2.710076 H 3.410416 1.178967 2.966686 H 2.678032 2.103369 1.637968 TS14 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.1268126 7000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.14990019000 a.u Ru 0.892163 0.380163 0.137152 O 0.079215 1.592030 1.566429 O 1.124070 1.233810 0.295852 N 3.684904 1.153126 0.008843

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263 N 3.716557 0.972364 0.503815 C 2.885637 0.066938 0.165815 C 5.075333 0.936774 0.400300 C 3.093327 2.484617 0.177042 C 2.966134 3.204905 1.190610 C 2.296542 4.582252 1.003864 C 3.130132 5.440347 0.032932 C 3.224050 4.720138 1.327546 C 3.941901 3.366368 1.124802 C 1.801652 4.497470 1.889987 C 0.976286 3.613202 0.913707 C 1.710521 2.251524 0.817255 C 0.882908 4.373048 0.429479 C 3.408265 2.345 875 0.772733 C 3.219601 2.742478 2.115593 C 2.961199 4.087011 2.386641 C 3.340979 1.752368 3.252902 C 5.143549 0.591032 0.461315 C 3.425978 3.300090 0.260904 C 2.912016 5.051476 1.371341 C 3.160379 4.638761 0.061795 C 3.761805 2.948985 1.693685 C 2.598397 6.494684 1.690480 H 1.911685 1.960765 1.857837 H 5.776643 1.362531 0.321834 H 5.269603 1.397313 1.378878 H 2.369022 2.586364 1.870459 H 3.961678 3.332646 1.640242 H 2.230972 5.083987 1.978438 H 4.137079 5.615109 0.439011 H 2.661287 6.425558 0.093305 H 3.807375 5.329990 2.030349 H 4.073411 2.848007 2.084481 H 4.944 904 3.548414 0.710287 H 1.857147 4.021633 2.879094 H 1.306823 5.468976 2.031311 H 0.029157 3.465331 1.324550 H 0.268512 3.839164 1.154846 H 0.404732 5.347891 0.258776 H 2.804217 4.393367 3.4 18913 H 4.387670 1.460242 3.412980 H 2.782545 0.829285 3.069921 H 2.980405 2.190912 4.188257 H 5.671163 0.966277 1.342662 H 5.620729 1.021077 0.429747 H 3.158187 5.376602 0.738235 H 4.737608 3.368002 1.971792 H 3.026261 3.369816 2.388551 H 3.802345 1.870820 1.859502 H 1.517999 6.647631 1.812302 H 2.935197 7.163884 0.892447 H 3.076101 6.811240 2.624370 C 0.910502 0.568414 1.761352 H 1.654156 1.306123 2.081922 C 0.100071 0.338497 2.841164 H 1.070005 0.051285 2.435319 H 0.288308 0.491644 3.459156 N 1.127211 1.801979 0.852243 O 2.048397 2.508967 1.228471 O 0.192847 1.533036 3.642072 C 0.148847 1.953805 0.033048 H 0.871213 2.617153 0.425168 C 1.360569 2.185034 0.100946 H 1.584813 3.266549 0.135633 C 1.292144 1.569210 1.548144 H 1.358748 2.379612 2.296740 C 0.202582 1.303685 1.277008 H 0.992196 1.318580 2.016085 O 2.147715 1.564794 0.873148 O 2.238799 0.587193 1.853405 C 3.548393 1.844363 0.725498 C 2.305058 0.219077 3.242609 C 4.325776 0.996 758 1.700701 C 5.090418 1.585394 2.713953 C 4.296792 0.402602 1.590841 C 5.824238 0.795562 3.603285 H 5.110424 2.668676 2.810437 C 5.022795 1.190871 2.484060 H 3.699475 0.866917 0.811716 C 5.790042 0.594835 3.490289 H 6.415295 1.266879 4.384244 H 4.994049 2.273340 2.390066 H 6.358009 1.212365 4.181493 C 3.714668 0.189522 3.594934 C 4.101779 1.534430 3.568552 C 4.662162 0.782760 3.943531 C 5.411800 1.899293 3.885821 H 3.375734 2.289221 3.282950 C 5.971540 0.421353 4.259761 H 4.369080 1.830502 3.970626 C 6.348512 0.923813 4.232212 H 5.700465 2.946832 3.860414 H 6.695 255 1.185623 4.531417 H 7.367542 1.208958 4.480994 H 2.007031 1.084886 3.854139 H 1.595725 0.594550 3.431285 H 3.729897 2.914632 0.914034 H 3.851653 1.617519 0.303055 C 1.105988 1.655483 4.6 47106 O 1.146936 2.696200 5.259721 C 2.007920 0.472601 4.931623 H 1.430449 0.440740 5.113452 H 2.676838 0.279543 4.086343 H 2.605752 0.705727 5.812944 8 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494 .15867579000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.19070325000 a.u

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264 Ru 1.756545 0.142091 0.318847 O 1.972550 1.754624 2.673108 O 1.528667 0.387583 2.456065 N 3.585039 0.162477 1.902264 N 1.623447 0.046092 2.866377 C 2.256904 0.023979 1.659168 C 3.898831 0.457422 3.305259 C 4.511253 0.390794 0.791227 C 4.830552 1.902119 0.641585 C 5.754775 2.130372 0.570703 C 7.063285 1.338209 0.3792 40 C 6.738580 0.164257 0.250820 C 5.838017 0.384001 0.984859 C 6.009350 0.642644 1.524172 C 4.687082 0.151876 1.708672 C 3.806544 0.118962 0.478423 C 5.029833 1.651694 1.841365 C 0.233399 0 .192828 3.136968 C 0.648178 0.901587 3.247332 C 2.004095 0.641868 3.473087 C 0.177164 2.337272 3.165744 C 2.568306 0.129909 3.999513 C 0.219172 1.509780 3.360779 C 2.498718 0.657901 3.618779 C 1.584469 1.715977 3.583860 C 0.724689 2.692081 3.410532 C 3.978414 0.911366 3.783966 H 3.675131 1.231416 0.383406 H 4.727677 0.156433 3.668445 H 4.176535 1.512590 3.425957 H 3.891623 2.456076 0.514352 H 5.313805 2.271170 1.557172 H 5.978838 3.201918 0.651577 H 7.597065 1.688347 0.515942 H 7.730960 1.505800 1.234643 H 7.667068 0.735038 0.119316 H 5.619752 1.451870 1.121536 H 6.360316 0.037826 1.888700 H 5.800589 1.719726 1.459972 H 6.654123 0.494114 2.401021 H 4.183824 0.200216 2.613903 H 4.117273 2.229545 2.008647 H 5.673258 1.800068 2.719273 H 2.693275 1.481 964 3.528507 H 0.080100 2.766717 4.172269 H 0.792567 2.430313 2.672075 H 0.897386 2.955095 2.619770 H 2.250766 0.900677 4.707698 H 2.603683 0.829177 4.531483 H 1.943322 2.732974 3.727347 H 1.043153 2.890682 4.443172 H 0.232343 3.600475 3.048838 H 1.627398 2.534106 2.814777 H 4.474180 0.969244 2.806148 H 4.168818 1.855802 4.303945 H 4.462163 0.106578 4.348014 C 0.516688 1.756212 0.120145 H 0.565671 2.259727 0.843796 C 0.519316 2.783133 1.233937 H 0.487418 2.325270 2.221313 H 1.422577 3.401637 1.161960 N 1.806182 0.648165 3.220479 O 1.871620 0.460394 4.432112 O 0.647 072 3.622089 1.020871 C 0.103079 0.915108 0.179004 H 0.071561 1.509435 0.715454 C 0.852408 1.258078 1.324684 H 0.382063 1.597332 2.252153 C 1.379186 0.216574 1.356917 H 1.097266 0.742360 2.2 77217 C 0.514346 0.629457 0.119620 H 1.104677 0.660078 0.797157 O 1.777015 2.217718 0.863097 O 2.761387 0.303908 1.123832 C 2.641176 2.717354 1.880373 C 3.257807 1.634418 1.247736 C 3.687710 3.609516 1.255490 C 4.131093 4.757070 1.921685 C 4.263170 3.276219 0.021796 C 5.138733 5.554211 1.374434 H 3.682982 5.031371 2.874319 C 5.264616 4.076179 0.529727 H 3.910717 2.391753 0.499553 C 5.708160 5.216074 0.145796 H 5.471639 6.442984 1.904293 H 5.701689 3.808950 1.488819 H 6.489182 5.837678 0.284296 C 4.693481 1.730520 0.788468 C 5.475272 0.603234 0.519415 C 5.257747 3.006988 0.647759 C 6.805750 0.751378 0.114557 H 5.043639 0.385816 0.627553 C 6.586068 3.151446 0.250107 H 4.646851 3.884633 0.851741 C 7.365447 2.022346 0.019374 H 7.404528 0.132534 0.091046 H 7.012420 4.146060 0.146350 H 8.400669 2.134563 0.331335 C 1.047325 4.548613 1.932499 O 2.105307 5.109130 1.756694 C 0.137539 4.823024 3.113154 H 0.877218 5.077561 2.788690 H 0.060008 3.94 3540 3.762630 H 0.558338 5.651272 3.683656 H 3.176712 1.952944 2.301671 H 2.640034 2.327362 0.664614 H 3.125664 1.875071 2.394577 H 2.057284 3.275514 2.629484

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265 9 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.15863628000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.18745618000 a.u Ru 1.480512 0.143687 0.370243 O 2.714712 0.704146 2.491716 O 1.069990 0.718935 2.439404 N 3.130900 0.588880 1.950029 N 1.731583 0.961602 2.609828 C 2.104387 0.196435 1.539796 C 3.371878 0.531918 3.393485 C 3.598222 1.654271 1.059647 C 2.820204 2.972323 1.312680 C 3.245249 4.036527 0.282675 C 4.756113 4.30719 4 0.431990 C 5.539594 2.999960 0.191671 C 5.109109 1.939461 1.231608 C 5.242905 2.490219 1.233751 C 3.725093 2.206410 1.387772 C 3.346109 1.118440 0.366595 C 2.941384 3.510717 1.135358 C 0. 928794 2.153728 2.613613 C 0.341436 2.109159 3.224464 C 1.092141 3.286439 3.289790 C 0.892620 0.831831 3.816925 C 2.630836 0.756175 3.769476 C 1.456314 3.365293 2.122113 C 0.610975 4.500146 2.785254 C 0.664691 4.517352 2.216454 C 2.812939 3.458046 1.460764 C 1.453673 5.753027 2.843931 H 4.003508 0.247895 0.515920 H 4.439522 0.489485 3.624300 H 2.945696 1.413198 3.892819 H 1.743965 2.777917 1.238514 H 3.020632 3.332632 2.332093 H 2.683340 4.961697 0.466726 H 4.972555 4.702230 1.434853 H 5.076390 5.071681 0.288465 H 6.615528 3.187959 0.302588 H 5.677415 1.010362 1.092154 H 5.324581 2.309488 2.245119 H 5.816054 1.577044 1.441779 H 5.560540 3.242128 1.969767 H 3.539397 1.857990 2.407150 H 1.865469 3.329968 1.251650 H 3.223059 4.265390 1.882443 H 2.07 5256 3.255648 3.754697 H 0.286680 0.477820 4.660462 H 0.921532 0.017063 3.086265 H 1.910086 0.987817 4.187193 H 2.058063 0.672421 4.696655 H 3.312694 1.611558 3.864304 H 1.064120 5.453417 1. 831946 H 3.508302 2.691070 1.811387 H 3.262527 4.438273 1.648648 H 2.725380 3.347795 0.372478 H 2.093736 5.840663 1.956046 H 0.831044 6.652711 2.884734 H 2.111989 5.753365 3.719222 C 0.345491 1.620552 0.655153 H 0.563174 2.359876 0.109057 C 0.272780 2.329803 1.995253 H 0.695789 2.849244 2.078231 H 0.364893 1.668083 2.853806 N 1.952205 0.065460 3.136185 O 1.992170 0.196594 4.35561 6 O 1.304994 3.324713 1.966664 C 0.170330 0.937910 0.238427 H 0.416713 1.142601 1.283816 C 1.191236 1.521236 0.747988 H 0.743202 2.092206 1.571362 C 1.666453 0.101273 1.202748 H 1.446795 0. 095684 2.260248 C 0.709031 0.657822 0.232717 H 1.206846 0.984268 0.682373 O 2.134487 2.299968 0.054105 O 3.028056 0.110127 0.923411 C 3.023221 3.018020 0.905823 C 3.523652 1.351040 1.398141 C 4.048673 3.751201 0.072776 C 4.582753 4.963118 0.525767 C 4.517042 3.212334 1.132291 C 5.574267 5.621487 0.203519 H 4.219131 5.397183 1.454849 C 5.502667 3.874127 1.866511 H 4.093306 2.280810 1.493124 C 6.037139 5.078638 1.403657 H 5.977764 6.562370 0.161639 H 5.853203 3.447913 2.803211 H 6.804642 5.592808 1.976131 C 4.997604 1.491825 1.082835 C 5.721853 0.474782 0.454610 C 5.655232 2.676622 1.440723 C 7.084280 0.642039 0.190447 H 5.219836 0.444085 0.173632 C 7.014002 2.842377 1.177754 H 5.100388 3.475092 1.930682 C 7.734507 1.822446 0.549890 H 7.635843 0.15 7709 0.296991 H 7.510339 3.766378 1.462744 H 8.794095 1.949120 0.344394 H 3.362662 1.421276 2.488022 H 2.964863 2.184244 0.939694 H 3.525545 2.314844 1.585631 H 2.454888 3.730165 1.525682 C 1.894872 3.832441 3.088462 O 2.747197 4.675060 2.941745

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266 C 1.448557 3.312806 4.438556 H 1.782066 2.278844 4.582997 H 0.359197 3.338332 4.552442 H 1.906176 3.940279 5.204128 10 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.18818054000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.19723348000 a.u Ru 1.510108 0.519511 1.011510 O 1.798119 1.441354 1.978156 O 0.228122 0.153506 2.748344 N 3.369441 2.227736 0.374074 N 3.523922 0.253788 1.331390 C 2.896165 0.949280 0.353850 C 4.230043 2.488592 1.532400 C 2.608575 3.245194 0.358165 C 1.560453 3.925454 0.560791 C 0.690874 4.895172 0.263397 C 1.590389 5.972204 0.901462 C 2.630563 5.294450 1.817747 C 3.510256 4.336759 0.978310 C 1.890242 4.511286 2.924939 C 0.990955 3.419406 2.285107 C 1.900856 2.473920 1.489564 C 0.040232 4.099 081 1.362877 C 3.456569 1.160444 1.580472 C 2.795555 1.606901 2.739670 C 2.795206 2.977312 3.017414 C 2.107698 0.649488 3.685718 C 4.579664 1.060584 1.980850 C 4.122580 2.063014 0.728231 C 3.429704 3.903796 2.186230 C 4.087240 3.422993 1.048349 C 4.860409 1.603688 0.508742 C 3.400647 5.381345 2.490779 H 2.701211 2.116170 2.187874 H 5.112198 3.074826 1.260184 H 3.678317 3.034377 2.309974 H 0.935236 3.153928 1.023675 H 2.068573 4.472733 1.367156 H 0.043356 5.371295 0.399844 H 2.095668 6.556169 0.119067 H 0.981883 6.678024 1.482841 H 3.273546 6.057795 2.274844 H 4.277 262 3.865505 1.607372 H 4.034212 4.905109 0.195662 H 2.611970 4.047965 3.611596 H 1.279469 5.202607 3.522061 H 0.475728 2.857420 3.073828 H 0.689742 3.344454 0.905401 H 0.681938 4.769823 1.9 50804 H 2.282364 3.329883 3.909744 H 2.825912 0.045419 4.257151 H 1.451203 0.048475 3.156470 H 1.499959 1.198226 4.411208 H 4.560196 0.931539 3.065466 H 5.564990 0.742247 1.614821 H 4.587498 4.129034 0.389283 H 5.397136 0.662030 0.349092 H 5.590065 2.357844 0.819590 H 4.169281 1.449295 1.345211 H 2.957597 5.578182 3.472675 H 2.815456 5.908678 1.729045 H 4.411187 5.808495 2.484220 C 1.140299 3.050130 0.921754 H 1.049149 3.600090 1.857246 C 0.744426 3.850432 0.288519 H 1.569418 4.515039 0.586573 H 0.494924 3.217109 1.142141 N 0.833053 1.277446 2.835134 O 0.530337 2.1 40014 3.638079 O 0.386923 4.659390 0.085169 C 0.184972 0.581342 0.243677 H 0.392490 0.602988 1.320431 C 1.312433 0.550661 0.016432 H 1.558892 1.109916 0.928557 C 1.850542 0.887851 0.230751 H 1.378821 1.277466 1.140921 C 1.607081 1.795440 0.949040 H 1.897039 1.366454 1.905991 O 1.933439 1.152951 1.121245 O 3.259698 0.737729 0.468638 C 3.048127 2.014814 0.847179 C 3.891850 1.886943 1.027379 C 3.882790 2.131196 2.098056 C 4.692274 1.056289 2.492676 C 3.855622 3.285466 2.886640 C 5.460688 1.138896 3.652526 H 4.713483 0.161180 1.876600 C 4.626879 3.372605 4.048575 H 3.228086 4.122605 2.588097 C 5.430055 2.298598 4.433540 H 6.088885 0.301941 3.946795 H 4.599088 4.276945 4.651082 H 6.032006 2.363973 5.336303 C 5.333891 1.552112 1.319884 C 6.374799 2.223644 0.670788 C 5.648148 0.552823 2.251728 C 7.707839 1.910934 0.949542 H 6.141025 2.996454 0.058141 C 6.976609 0.234257 2.528065 H 4.843198 0.023362 2.755048 C 8.010745 0.914932 1.878067 H 8.50 6433 2.442300 0.438573 H 7.207549 0.542416 3.252435 H 9.046624 0.668341 2.095526 H 2.682064 3.005043 0.536230 H 3.646612 1.593221 0.034107

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267 H 3.830083 2.737907 0.334215 H 3.367135 2.173322 1. 954746 C 1.028433 5.439894 0.825519 O 1.931529 6.148611 0.439903 C 0.590212 5.370624 2.272871 H 0.797041 4.381440 2.697363 H 0.483086 5.560284 2.384110 H 1.148548 6.123345 2.830082 11 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.18507311000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.20414787000 a.u Ru 0.595226 1.036731 1.001929 O 2.144199 0.061270 2.210468 O 0.074606 0.431377 2.651238 N 0.682238 3.532085 0.430758 N 2.496071 2.425624 1.001331 C 1.372690 2.375491 0.242610 C 1.243753 4.356473 1.505195 C 0.698294 3.590749 0.060368 C 1.699134 3.197501 1.056279 C 3.129368 3.141038 0.485883 C 3.509434 4.522485 0.082342 C 2.515082 4.908903 1.196908 C 1.085181 4.984230 0.606884 C 2.580810 3.847795 2.318171 C 2.184461 2.458151 1.750806 C 0.749367 2.570815 1.216830 C 3.1 71519 2.077074 0.629080 C 3.630289 1.544219 0.924189 C 3.865388 0.646986 1.985098 C 5.016653 0.142861 1.946090 C 2.898485 0.517868 3.139219 C 2.644877 3.740596 1.664000 C 4.533478 1.653195 0 .148301 C 5.937202 0.062929 0.893006 C 5.673295 0.839638 0.140127 C 4.298345 2.600170 1.302274 C 7.163007 0.944944 0.874749 H 0.119009 2.988176 2.043682 H 1.275163 5.414771 1.230857 H 0.648624 4.255435 2.422888 H 1.421204 2.221165 1.467000 H 1.649041 3.931157 1.873179 H 3.823803 2.862333 1.288882 H 3.497114 5.277733 0.716259 H 4.531321 4.499764 0.484575 H 2.781247 5.892385 1.6056 29 H 0.364307 5.290878 1.376758 H 1.054577 5.741842 0.190192 H 1.909914 4.122815 3.143730 H 3.598216 3.811546 2.732226 H 2.221050 1.708862 2.551236 H 2.913689 1.098412 0.210817 H 4.187497 2 .001010 1.041392 H 5.201835 0.840680 2.759834 H 2.699183 1.479324 3.627215 H 1.931992 0.122296 2.806513 H 3.295064 0.163269 3.897988 H 2.947489 3.620845 2.707479 H 3.415403 4.330813 1.150698 H 6.376262 0.920617 0.966404 H 3.946012 3.584196 0.974180 H 5.220796 2.747455 1.872202 H 3.546154 2.195473 1.989501 H 7.706610 0.888933 1.825610 H 6.879355 1.993340 0.721246 H 7.851365 0.654378 0.074503 C 1.312163 3.685573 1.641670 H 1.702929 3.873629 2.641052 C 1.913383 4.550503 0.570593 H 1.527467 5.572395 0.653582 H 1.679604 4.194404 0.435780 N 1.310863 0.640987 2.924038 O 1.685195 1.433034 3.762170 O 3.334969 4.697958 0.758194 C 0.117410 0.071135 0.373306 H 0.119923 0.258097 1.428698 C 1.080885 1.095240 0.222012 H 1.668366 0.998535 0.700112 C 0.304900 2.44 4818 0.147161 H 0.471917 2.315471 0.620396 C 0.339220 2.783263 1.473634 H 0.061506 2.268530 2.342863 O 1.942509 1.007431 1.360022 O 1.123222 3.559273 0.237847 C 3.196420 1.700816 1.258125 C 1.343377 3.742347 1.645278 C 4.036605 1.324519 2.452559 C 3.815453 1.936805 3.693272 C 5.033501 0.346718 2.352046 C 4.571899 1.579293 4.809417 H 3.045300 2.699752 3.780340 C 5.796401 0.011947 3.465322 H 5.216070 0.131119 1.392152 C 5.565816 0.603525 4.697039 H 4.390892 2.064634 5.765011 H 6.571425 0.768187 3.370338 H 6.159917 0.327917 5.564492 C 2.705145 3.279596 2.123876 C 3.86 7494 3.873003 1.609949 C 2.828308 2.282336 3.098687 C 5.127096 3.466091 2.047886 H 3.779949 4.654299 0.858536 C 4.090310 1.878712 3.545185 H 1.933594 1.816949 3.503474 C 5.241400 2.465600 3. 018461 H 6.019653 3.932939 1.639282

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268 H 4.170721 1.106101 4.305629 H 6.222751 2.152146 3.364996 H 3.700279 1.415713 0.324342 H 3.022401 2.781714 1.225565 H 1.248951 4.823329 1.809641 H 0.552734 3.244910 2.221797 C 4.226376 3.790410 0.270421 O 5.387228 3.912836 0.591585 C 3.723439 2.708107 0.661425 H 2.973422 2.076184 0.175889 H 3.273685 3.132805 1.566209 H 4.566505 2.082541 0.951117 12 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.18095563000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.19481726000 a.u Ru 1.676494 0.271723 0.926163 O 1.957870 1.340215 2.382066 O 0.393715 0.112202 2.785820 N 3.577404 1.401623 0.918422 N 3.652805 0.780178 1.195360 C 3.059185 0.218939 0.494466 C 4.444425 1.248231 2.091314 C 2.870595 2.627219 0.527504 C 1.843903 3.042805 1.613153 C 1.0 21749 4.251187 1.124379 C 1.969848 5.432097 0.839787 C 2.990690 5.019765 0.241484 C 3.822716 3.816167 0.266501 C 2.227906 4.639800 1.530211 C 1.279972 3.442693 1.249461 C 2.148772 2.264246 0 .787989 C 0.267882 3.850292 0.159434 C 3.549974 2.185661 0.915162 C 2.821517 3.001131 1.802468 C 2.751313 4.372377 1.540680 C 2.133308 2.428343 3.019544 C 4.726601 0.265713 2.072474 C 4.221964 2.735232 0.192407 C 3.386467 4.947914 0.435110 C 4.122012 4.113509 0.410277 C 5.026988 1.885123 1.147662 C 3.266936 6.427463 0.153222 H 2.943928 2.113281 1.562753 H 5.354815 1.848073 2.0044 07 H 3.917641 1.552745 3.005757 H 1.179530 2.200203 1.830897 H 2.371933 3.300713 2.542202 H 0.300517 4.530652 1.902838 H 2.490816 5.731240 1.760433 H 1.397036 6.305420 0.499651 H 3.669825 5 .856823 0.449278 H 4.577512 3.527380 0.477335 H 4.358542 4.098533 1.184776 H 2.935424 4.379149 2.329390 H 1.650281 5.504424 1.885944 H 0.750194 3.170475 2.170781 H 0.413937 3.021764 0.060070 H 0.341582 4.692115 0.516443 H 2.186294 5.006969 2.220237 H 2.852718 2.066952 3.766324 H 1.490623 1.580518 2.760730 H 1.515102 3.188410 3.506408 H 4.678760 0.724363 3.063426 H 5.707670 0.4963 66 1.636131 H 4.636864 4.543749 1.266754 H 5.582922 1.091898 0.636951 H 5.746860 2.501536 1.694947 H 4.373389 1.407255 1.886135 H 3.129691 7.002881 1.074822 H 2.404442 6.636468 0.493327 H 4.155886 6.810870 0.358867 C 2.897667 2.786679 1.427750 H 2.783954 3.243904 2.410655 C 4.202364 3.145890 0.762800 H 4.995823 2.457201 1.070800 H 4.141843 3.111088 0.323800 N 1.001385 0.949676 3.176300 O 0.714489 1.549048 4.188665 O 4.665180 4.431778 1.226485 C 0.328269 0.092723 0.290661 H 0.498046 0.121758 1.354139 C 1.152762 0.198063 0.024758 H 1.310025 0.795042 0.932545 C 1.78 7649 1.211998 0.286611 H 1.089881 1.745001 0.954384 C 1.911550 1.989835 0.999563 H 1.057147 1.866895 1.661688 O 1.726006 0.858355 1.104172 O 3.059660 1.132525 0.924025 C 2.985756 1.502458 0. 878980 C 3.064760 0.953620 2.350501 C 3.425141 2.153044 2.167607 C 3.547515 1.385921 3.335195 C 3.734873 3.515919 2.218897 C 3.972632 1.971813 4.526446 H 3.302001 0.327932 3.300612 C 4.168734 4.104509 3.409888 H 3.638139 4.120854 1.320067 C 4.287200 3.333727 4.566570 H 4.063232 1.366306 5.424725 H 4.408568 5.164479 3.433199 H 4.622035 3.789331 5.494861 C 3.569748 0.411704 2.76952 9 C 4.834833 0.851552 2.353189 C 2.801169 1.239595 3.596069 C 5.316379 2.099897 2.744646 H 5.439377 0.212311 1.714333

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269 C 3.287220 2.487641 3.997177 H 1.818298 0.908084 3.919665 C 4.542442 2. 921797 3.570001 H 6.297262 2.430204 2.412546 H 2.681680 3.119218 4.642132 H 4.919859 3.892850 3.879792 H 2.886486 2.252518 0.080612 H 3.724033 0.764386 0.544801 H 3.732323 1.731053 2.746639 H 2.065499 1.131551 2.763086 C 4.192815 5.596104 0.702575 O 4.559716 6.638646 1.190378 C 3.249221 5.521525 0.484689 H 2.375302 4.898209 0.269660 H 3.753877 5.094446 1.359333 H 2.929437 6.536229 0.722918 TS9E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.12113793000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.14836257000 a.u Ru 1.586909 0.212936 0.510984 O 1.568941 1.492374 2.047424 O 1.14628 4 0.551838 2.641765 N 3.660534 0.587859 1.355876 N 1.785929 0.807389 2.482543 C 2.311272 0.449078 1.263827 C 4.108617 1.224301 2.598096 C 4.468252 0.563011 0.128157 C 4.620829 1.994477 0.451 799 C 5.412691 1.947903 1.774585 C 6.803984 1.332969 1.526148 C 6.635417 0.095286 0.969627 C 5.878784 0.020621 0.377185 C 5.845587 0.948120 1.988646 C 4.436571 0.333100 2.217347 C 3.711962 0.356313 0.849317 C 4.634033 1.088648 2.788534 C 0.432655 1.191156 2.782759 C 0.000233 2.480574 2.392507 C 1.299814 2.874275 2.710010 C 0.912126 3.425828 1.642129 C 2.837506 1.176182 3.457912 C 0.399976 0.357950 3.548776 C 2.176204 2.039967 3.416974 C 1.699242 0.800067 3.840190 C 0.044425 0.989214 4.074395 C 3.588790 2.485131 3.712927 H 3.864072 1.374687 0.465810 H 4.939415 0.673 657 3.048379 H 4.445747 2.252252 2.409984 H 3.627533 2.423347 0.625572 H 5.142649 2.639247 0.270233 H 5.523392 2.969539 2.161313 H 7.376430 1.950312 0.818787 H 7.375654 1.306957 2.463548 H 7.622397 0.545160 0.798133 H 5.788127 1.019337 0.826168 H 6.449606 0.604140 1.080864 H 5.754367 1.981874 1.627164 H 6.399613 0.990934 2.937131 H 3.885849 0.948804 2.938037 H 3.678542 1.565130 3.015450 H 5.194709 1.026691 3.731820 H 1.639004 3.860939 2.400396 H 1.841544 3.619434 2.191615 H 1.200569 3.031576 0.660771 H 0.418141 4.388986 1.483322 H 2.601849 2.134136 3.930103 H 2.901831 0.418948 4.249481 H 2.351836 0.149031 4.417787 H 1.125494 1.036711 4.230173 H 0.441048 1.200645 5.032612 H 0.224154 1.810601 3.398166 H 3.602862 3.446468 4.241249 H 4.160123 2.616754 2.785578 H 4.118331 1.753255 4.330265 N 1.277103 0.680861 3.001598 O 1.135727 1.042965 4.154562 C 1.324476 1.967349 0.099024 H 0.878504 2.663908 0.629656 C 1.753351 2.668830 1.348668 H 1.78 5537 1.992999 2.201963 H 2.782696 3.023643 1.181849 O 0.889915 3.747714 1.752113 C 1.029516 5.027361 1.294237 O 0.216915 5.849409 1.637560 C 2.216507 5.351378 0.403553 H 3.162245 5.221480 0. 943104 H 2.252951 4.717491 0.488636 H 2.126288 6.394426 0.099785 C 0.700313 0.771387 0.202698 H 0.742163 1.141694 1.219723 C 1.525485 1.266484 0.987881 H 1.017116 1.958030 1.674954 C 1.519986 0.233045 1.493232 H 1.167578 0.419612 2.513697 C 0.579260 0.525765 0.309556 H 0.466064 1.463457 0.216274 O 2.749488 1.787072 0.558517 O 2.802537 0.805130 1.311197 C 3.582908 2.239453 1.628985 C 2.858531 2.178589 1.694390 C 4.961089 2.528536 1.089020 C 5.557221 3.781307 1.259838 C 5.669414 1.519903 0.420111 C 6.846543 4.026368 0.779753 H 5.009748 4.571964 1.768193 C 6.9529 83 1.765085 0.064690

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270 H 5.201227 0.549657 0.282859 C 7.546349 3.018603 0.115869 H 7.298307 5.005125 0.918851 H 7.493693 0.976717 0.582342 H 8.548023 3.207884 0.261588 C 4.239779 2.714158 1.40 4184 C 5.367417 2.116720 1.984236 C 4.418756 3.813575 0.557854 C 6.645272 2.608780 1.720917 H 5.239475 1.257192 2.636274 C 5.697123 4.314876 0.298384 H 3.550348 4.283307 0.100919 C 6.813464 3.711813 0.878751 H 7.510590 2.133590 2.175335 H 5.819188 5.172925 0.357619 H 7.809291 4.097697 0.677358 H 2.105597 2.764657 1.147506 H 2.621093 2.266283 2.767958 H 3.145756 3.140382 2.087780 H 3.635379 1.459267 2.401260 TS10E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.14368577000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.17782002000 a.u Ru 1.728487 0.064940 0.579895 O 2.070463 2.679687 2.375646 O 1.728950 0.514576 2.667671 N 3.384260 0.507469 1.758601 N 1.369697 0.957674 2.490138 C 2.088683 0.613069 1.377662 C 3.622499 0.757200 3.184892 C 4.379314 0.095108 0.868258 C 4.6596 86 1.563822 1.288554 C 5.658454 2.212712 0.311034 C 6.975840 1.411310 0.314961 C 6.693875 0.042463 0.117565 C 5.713627 0.691322 0.885411 C 6.075680 0.043895 1.530975 C 4.745866 0.756413 1.52 8448 C 3.779347 0.078122 0.544859 C 5.040014 2.209387 1.098660 C 0.012736 1.424543 2.566169 C 1.033807 0.537218 2.883481 C 2.342983 1.036780 2.908467 C 0.811112 0.915219 3.241693 C 2.208142 1.065427 3.704903 C 0.239732 2.807837 2.424489 C 2.634786 2.381324 2.670777 C 1.562324 3.256612 2.461964 C 0.885215 3.813188 2.292724 C 4.062535 2.871517 2.634168 H 3.676911 1.005470 0.865592 H 4.316085 1.593535 3.325846 H 4.057026 0.124649 3.666764 H 3.713218 2.118174 1.289374 H 5.065389 1.588633 2.309792 H 5.851952 3.244678 0.631971 H 7.431447 1.427710 1.315632 H 7.697599 1.87 2677 0.371946 H 7.629835 0.616512 0.119936 H 5.523715 1.739818 0.617487 H 6.156352 0.685309 1.892404 H 5.896605 1.075278 1.866217 H 6.778830 0.405057 2.245769 H 4.322730 0.743700 2.536172 H 4.115822 2.793752 1.119407 H 5.732989 2.670215 1.815580 H 3.155859 0.345809 3.122182 H 1.248038 1.126592 4.225330 H 0.250075 1.171825 3.284205 H 1.294258 1.585540 2.522243 H 1.865745 0.350506 4.461713 H 2.130362 2.068834 4.134721 H 1.761652 4.318054 2.329262 H 1.312869 4.055195 3.275176 H 0.518770 4.754697 1.871334 H 1.704645 3.451220 1.664695 H 4.509697 2.688788 1.648349 H 4.12 4219 3.946974 2.829817 H 4.683063 2.352846 3.373003 N 2.078620 1.697892 3.136790 O 2.380893 1.753998 4.327569 C 0.217126 1.401176 1.477170 H 0.418457 1.250398 2.537584 C 0.133199 2.850336 1. 082400 H 0.143691 2.977540 0.001297 H 0.947862 3.426819 1.532114 O 1.149577 3.315977 1.586403 C 0.490672 1.229045 0.000858 H 0.373551 1.429363 1.067917 C 0.541713 1.982612 0.824117 H 0.076208 2.722543 1.486295 C 1.166869 0.788583 1.602611 H 0.801324 0.787652 2.636538 C 0.605673 0.435044 0.859590 H 1.162695 0.709162 0.034425 O 1.429574 2.603921 0.089909 O 2.578471 0.792251 1.56300 2 C 2.218777 3.654871 0.478196 C 3.166066 0.141965 2.489158 C 3.301462 4.028268 0.503326 C 3.359211 5.304992 1.070184 C 4.275779 3.081690 0.854467 C 4.377141 5.640181 1.967408 H 2.603954 6.042512 0.807579 C 5.288972 3.412864 1.752945 H 4.230268 2.089577 0.414207 C 5.343260 4.694244 2.311033

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271 H 4.411734 6.637539 2.398210 H 6.042032 2.673318 2.013631 H 6.135995 4.952728 3.008463 C 4.566938 0.481515 2.044206 C 5.542580 0.519104 1.934209 C 4.909377 1.804923 1.737944 C 6.835928 0.205520 1.516660 H 5.283849 1.547660 2.172555 C 6.208700 2.120381 1.329286 H 4.165618 2.59 4263 1.826704 C 7.172281 1.117083 1.214062 H 7.582857 0.990914 1.434171 H 6.465144 3.152687 1.105419 H 8.182153 1.363274 0.895867 C 1.483582 4.628701 1.659213 O 2.625337 4.918456 1.935662 C 0.397533 5.660148 1.420336 H 0.075501 5.533091 0.440809 H 0.389679 5.577907 2.178869 H 0.848692 6.650799 1.480594 H 2.663870 3.306840 1.418225 H 1.577384 4.521294 0.701262 H 2.567787 1.058725 2.535852 H 3.164748 0.314100 3.491859 TS12E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.17806879000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.19492099000 a.u Ru 1.639685 0.036942 0.634496 O 2.154357 1.9 30751 1.826421 O 1.122194 0.287020 2.805836 N 3.882040 0.383491 1.140891 N 2.485201 0.931826 2.207503 C 2.677884 0.239461 1.056391 C 4.478241 0.292035 2.476290 C 4.215169 1.375171 0.115199 C 3.834512 2.803424 0.584790 C 4.037786 3.810253 0.561785 C 5.522741 3.806110 0.975473 C 5.920116 2.388310 1.435417 C 5.714742 1.387135 0.268714 C 5.043708 2.002530 2.647987 C 3.546521 1.984481 2.233250 C 3.416433 0.924409 1.125896 C 3.146663 3.391907 1.749525 C 1.435588 1.874896 2.475627 C 0.330275 1.467434 3.244496 C 0.646884 2.421521 3.557812 C 0.169899 0.042274 3.718949 C 3.654037 0.845214 3.108631 C 1.573396 3.210284 2.041961 C 0.545655 3.751422 3.141575 C 0.574590 4.124599 2.388326 C 2.755978 3.661259 1.214126 C 1.615756 4.762584 3.483719 H 3.912634 0.011826 1.501035 H 5.546113 0.060957 2.425451 H 4.356994 1.236830 3.023754 H 2.795310 2.821470 0.922746 H 4.459492 3.084283 1.444931 H 3.752755 4.813139 0.216885 H 6.149875 4.124926 0.130789 H 5.69 3103 4.523658 1.789270 H 6.978451 2.377192 1.726844 H 6.028345 0.378001 0.565805 H 6.338369 1.686912 0.586673 H 5.336529 1.017507 3.034924 H 5.204154 2.724675 3.461012 H 2.933520 1.696310 3. 094636 H 2.091585 3.399975 1.447967 H 3.253027 4.112534 2.572023 H 1.504166 2.113410 4.152270 H 0.564601 0.012214 4.528230 H 1.112266 0.377081 4.087422 H 0.185383 0.607635 2.910468 H 3.337634 0.629021 4.132927 H 4.201468 1.796186 3.114590 H 0.677229 5.158568 2.064485 H 3.713101 3.406348 1.683612 H 2.736098 4.747018 1.079329 H 2.752450 3.201450 0.219603 H 2.223251 5.012102 2.60403 1 H 1.178662 5.699439 3.848169 H 2.293795 4.382550 4.254150 N 1.585135 1.485615 2.893588 O 1.475578 2.152094 3.905672 C 1.203996 1.783853 1.237578 H 1.027687 1.687381 2.308544 C 1.214744 3. 183418 0.694604 H 1.406149 3.181308 0.380585 H 0.254798 3.678723 0.866694 O 2.293637 3.940199 1.282409 C 0.693881 1.355017 0.135452 H 1.016190 1.973816 0.985390 C 0.753047 1.717817 0.159385 H 0.769297 2.705588 0.652557 C 1.484027 0.714225 1.068777 H 1.013910 0.728639 2.062936 C 1.426649 0.685652 0.500564 H 1.645233 0.775330 0.562692 O 1.418841 1.802867 1.105370 O 2.835923 1.17289 1 1.177879 C 2.286205 2.932937 1.281560 C 3.577497 0.573304 2.241150 C 3.240377 2.635919 2.410140 C 3.123584 3.273337 3.649171 C 4.260260 1.691457 2.222199 C 4.013324 2.981379 4.686450

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272 H 2.333131 4.004959 3.802749 C 5.146691 1.395834 3.256244 H 4.350159 1.199169 1.257629 C 5.025631 2.041147 4.491271 H 3.914878 3.487268 5.643485 H 5.937506 0.666942 3.098700 H 5.720555 1.813310 5.295467 C 4.934010 1.229582 2.321432 C 5.039411 2.617466 2.490450 C 6.103479 0.466194 2.245711 C 6.289342 3.227441 2.581027 H 4.134391 3.216746 2.545445 C 7.357893 1.073844 2.344312 H 6.032 493 0.610587 2.110563 C 7.453099 2.455622 2.510701 H 6.357910 4.304478 2.710585 H 8.257772 0.467258 2.286395 H 8.427650 2.930912 2.585145 H 2.839980 3.107763 0.353465 H 1.686904 3.828641 1.5 07094 H 3.024635 0.710809 3.186109 H 3.684646 0.507335 2.078442 C 2.124906 4.762149 2.358797 O 3.104658 5.294827 2.822299 C 0.723993 4.989692 2.898269 H 0.087230 5.478824 2.151702 H 0.224117 4.063154 3.199899 H 0.811347 5.643982 3.766000 TS13E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.17634461000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.18796409000 a.u Ru 1.769820 0.194660 0.916032 O 1.31 9320 1.415101 2.302249 O 0.430565 0.515291 2.756755 N 4.240135 0.497937 0.523197 N 3.489855 1.529825 0.946167 C 3.234863 0.384466 0.270795 C 5.156293 0.017608 1.563755 C 4.000229 1.904142 0. 176020 C 3.421009 2.678022 1.388466 C 3.048369 4.113132 0.970746 C 4.310192 4.836656 0.458435 C 4.885301 4.069964 0.750572 C 5.270859 2.634215 0.315729 C 3.818703 4.026838 1.867437 C 2.552874 3.285492 1.358147 C 2.974628 1.859460 0.977287 C 1.984693 4.045929 0.143469 C 2.794705 2.780278 0.789765 C 1.894707 3.196476 1.787058 C 1.269670 4.440870 1.635949 C 1.561518 2.345278 2.991226 C 4.801005 1.480854 1.628150 C 3.078591 3.595460 0.325484 C 1.512932 5.264992 0.535552 C 2.425554 4.825360 0.430191 C 4.041724 3.163399 1.407024 C 0.807319 6.592521 0.382592 H 3.50379 4 1.427304 1.863126 H 6.202129 0.191740 1.294763 H 4.958269 0.521771 2.519158 H 2.537653 2.150091 1.763458 H 4.161748 2.705743 2.199789 H 2.642993 4.647752 1.839958 H 5.059252 4.902211 1.260 118 H 4.064237 5.866376 0.166108 H 5.783811 4.581498 1.119131 H 5.710759 2.080821 1.155926 H 6.030450 2.679432 0.478758 H 4.217623 3.520019 2.756607 H 3.561641 5.050785 2.172412 H 1.804585 3.245420 2.159380 H 1.085047 3.539567 0.227910 H 1.687584 5.060213 0.443457 H 0.573588 4.770707 2.404312 H 1.270801 2.975890 3.837587 H 2.401522 1.719444 3.306773 H 0.718693 1.675565 2.779105 H 4.722204 1.861348 2.650208 H 5.528950 2.100346 1.088846 H 2.637776 5.458068 1.289505 H 4.958895 2.721943 1.002162 H 4.328601 4.017369 2.028218 H 3.578177 2.418285 2.063443 H 0.001959 6.528 657 0.360635 H 1.495504 7.375760 0.044557 H 0.358258 6.919082 1.325929 N 0.558415 0.709996 3.098084 O 0.031875 1.197163 4.073885 C 2.611200 1.190745 1.772871 H 3.160101 0.484977 2.396177 C 2.739757 2.642471 2.128752 H 2.251215 3.267577 1.376516 H 2.263910 2.847263 3.093794 O 4.117038 3.075102 2.143129 C 0.730238 0.470735 0.572937 H 1.106005 0.217871 1.572214 C 0.714612 0.929638 0.738364 H 0.689384 2.008040 0.977249 C 1.631693 0.727933 0.484241 H 1.154221 1.203589 1.350403 C 1.841775 0.742826 0.778518 H 1.308308 1.450633 0.147928 O 1.225887 0.209770 1.866136 O 2.912700 1.339402 0.278606 C 2.091774 0.948980 2.736223 C 2.978629 2.705505 0.656654

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273 C 2.750469 0.013022 3.693299 C 2.553448 0.087975 5.073846 C 3.584789 1.025829 3.197864 C 3.183854 0.799020 5.950736 H 1.903641 0.867223 5.466642 C 4.209098 1.916265 4.069383 H 3.738170 1.110150 2.125390 C 4.011654 1.803681 5.449389 H 3.024656 0.706042 7.021994 H 4.854692 2.695905 3.673573 H 4.50 2625 2.495934 6.128501 C 4.383957 3.228367 0.455116 C 4.595709 4.604026 0.300147 C 5.486997 2.366991 0.460765 C 5.887084 5.113921 0.163382 H 3.744039 5.281825 0.285242 C 6.779016 2.876280 0. 315584 H 5.324124 1.299901 0.566236 C 6.984140 4.249464 0.169899 H 6.035535 6.184047 0.043649 H 7.626810 2.196141 0.316330 H 7.990735 4.643543 0.057627 H 2.849511 1.467718 2.138702 H 1.510804 1.703394 3.290849 H 2.270957 3.317229 0.072898 H 2.681735 2.805497 1.715472 C 4.880188 3.044699 3.268570 O 6.040353 3.371989 3.185877 C 4.233910 2.628942 4.580233 H 3.484181 3.362622 4.898907 H 3.733534 1.657578 4.514705 H 5.020119 2.581274 5.334084 TS14E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.14672098000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.17796074000 a.u Ru 1.739373 0.187711 0.477143 O 2.304979 1.075618 4.064270 O 1.325717 0.239497 2.616405 N 3.520773 0.113534 1.786942 N 1.527511 0.212437 2.715221 C 2.189984 0.149784 1.514587 C 3.834697 0.021161 3.216543 C 4.442092 0.332389 0.735720 C 4.617565 1.875782 0.803929 C 5.519310 2.360337 0.346208 C 6.899187 1.681760 0.224495 C 6.729686 0.149784 0.297765 C 5.832806 0.330639 0.864155 C 6.072397 0.223 374 1.639864 C 4.681662 0.454470 1.761686 C 3.795337 0.045483 0.609152 C 4.858951 1.984371 1.685952 C 0.163913 0.169598 2.986450 C 0.163185 1.548029 2.957152 C 1.478669 1.929278 3.215722 C 0.880474 2.607123 2.677707 C 2.463466 0.270538 3.863114 C 0.788820 0.780315 3.391697 C 2.472924 0.994360 3.535392 C 2.099614 0.343592 3.642450 C 0.473962 2.244907 3.603435 C 3.895835 1.440760 3.772462 H 3.728985 1.165493 0.667223 H 4.576477 0.770398 3.507371 H 4.237125 0.969212 3.463720 H 3.629865 2.349622 0.738534 H 5.057705 2.161108 1.769697 H 5.635026 3.449890 0.276064 H 7.38 0407 1.967277 0.721891 H 7.558571 2.022728 1.033428 H 7.710823 0.335444 0.213468 H 5.722331 1.423262 0.840004 H 6.296496 0.069262 1.826683 H 5.967068 1.313382 1.725747 H 6.709940 0.100239 2. 473733 H 4.261571 0.177893 2.725737 H 3.885785 2.479590 1.790590 H 5.481174 2.324159 2.524078 H 1.738001 2.984214 3.164110 H 1.702094 2.566356 3.404354 H 1.326256 2.502236 1.683405 H 0.435953 3.604412 2.738647 H 2.197185 0.485030 4.607676 H 2.407188 1.253111 4.346125 H 2.844433 1.082123 3.931556 H 0.857985 2.572841 4.576350 H 0.948733 2.874767 2.842395 H 0.599253 2.447534 3.58574 3 H 4.301684 1.935290 2.881635 H 4.546234 0.595023 4.015055 H 3.956123 2.161837 4.597256 N 2.175593 0.062356 3.608096 O 2.776397 1.054320 4.037118 C 0.556379 1.853041 0.593572 H 0.611378 2. 195152 1.629498 C 0.678861 2.980823 0.403088 H 0.830743 2.610950 1.413365 H 1.515801 3.636386 0.145484 O 0.557663 3.738066 0.480149 C 0.050262 0.799447 0.350095 H 0.229154 1.307951 0.569094 C 0.880384 1.160934 1.511873 H 0.386518 1.497657 2.428018 C 1.385718 0.318055 1.587051 H 1.087998 0.811440 2.520425 C 0.499663 0.795795 0.380726 H 1.055663 0.936951 0.547388

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274 O 1.819959 2.101926 1.045620 O 2.761752 0.455090 1.349089 C 2.681632 2.615250 2.061693 C 3.204875 1.806962 1.524933 C 3.834438 3.333438 1.402760 C 4.642901 2.649709 0.481967 C 4.126530 4.666561 1.704129 C 5.724410 3.292293 0.119412 H 4.414283 1.614114 0.247876 C 5.212740 5.311049 1.104716 H 3.500205 5.206085 2.411227 C 6.012954 4.625571 0.190765 H 6.350117 2.750212 0.824405 H 5.428472 6.34 7903 1.349588 H 6.857878 5.124608 0.276913 C 4.648555 1.948847 1.110943 C 5.609889 1.003881 1.492704 C 5.045621 3.065748 0.365430 C 6.946085 1.170167 1.127624 H 5.307072 0.133568 2.067208 C 6.385825 3.237501 0.011128 H 4.302211 3.803489 0.070663 C 7.338249 2.289222 0.387930 H 7.682286 0.427556 1.424613 H 6.682814 4.110186 0.564920 H 8.380437 2.420122 0.107968 H 3.073685 2.082808 2.585539 H 2.586563 2.489678 0.929694 H 3.057422 1.785348 2.675723 H 2.122659 3.296852 2.721742 C 0.834131 4.807540 0.315663 O 1.960525 5.248409 0.307446 C 0.286050 5.406385 1.144192 H 1.105170 5.759618 0.507503 H 0.702489 4.681499 1.851861 H 0.124161 6.250767 1.698348 TS15E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.12090332000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.14345546000 a.u Ru 0.760777 0.436046 0.065957 O 0.000853 0.969339 2.162837 O 1.211323 1.361811 0.408663 N 3.598864 1.025907 0.193420 N 3.512449 1.165442 0.079596 C 2.738186 0.026162 0.118356 C 4.997005 0.6 41601 0.400458 C 3.079868 2.357990 0.530774 C 3.086816 2.572183 2.067726 C 2.478819 3.947990 2.412171 C 3.291225 5.062341 1.724730 C 3.257284 4.846705 0.198225 C 3.910909 3.483965 0.128240 C 1.790228 4.871575 0.289082 C 0.984121 3.731277 0.393280 C 1.648212 2.398742 0.031778 C 1.020503 3.984659 1.917047 C 3.130840 2.523515 0.353580 C 2.926267 2.906573 1.698807 C 2.618513 4.240202 1.977268 C 3.056350 1.911498 2.830977 C 4.961991 0.860311 0.095498 C 3.108146 3.483187 0.675434 C 2.536990 5.207711 0.968557 C 2.801243 4.809969 0.342888 C 3.404377 3.146193 2.120283 C 2.1 79349 6.639223 1.293860 H 1.765954 2.475100 1.120530 H 5.663184 1.190012 0.271487 H 5.310537 0.848867 1.432416 H 2.507380 1.775030 2.547181 H 4.116410 2.515511 2.450428 H 2.504970 4.088546 3 .500851 H 4.330329 5.060353 2.084766 H 2.867732 6.044310 1.975422 H 3.825835 5.642471 0.301430 H 3.949695 3.322115 1.214257 H 4.947947 3.481632 0.240427 H 1.753069 4.761201 1.381863 H 1.342086 5.846918 0.051767 H 0.052143 3.756723 0.037794 H 0.430560 3.247483 2.463380 H 0.581127 4.969260 2.130613 H 2.453487 4.534618 3.011675 H 4.050785 1.448344 2.850261 H 2.329830 1.094793 2.755024 H 2.905068 2.405779 3.795148 H 5.471485 1.464380 0.851714 H 5.409563 1.095396 0.878384 H 2.779045 5.552349 1.138103 H 3.858292 4.005906 2.623824 H 2.497074 2.892327 2.682422 H 4.0911 19 2.301296 2.217184 H 1.090854 6.772648 1.349714 H 2.553017 7.329092 0.530289 H 2.592283 6.945751 2.261120 N 1.097058 1.442985 1.680173 O 1.951677 1.949913 2.390406 C 0.579556 0.167779 1.77 9414 H 0.445867 0.311376 2.145023 C 1.551178 0.119519 2.880389 H 2.488212 0.531255 2.509062 H 1.783836 0.841165 3.367160 O 1.080535 1.087744 3.840982 C 0.087792 1.625979 0.787553 H 0.636865 1.884114 1.548155 C 1.603811 1.896887 0.815180 H 1.763072 2.911778 1.220960

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275 C 1.529678 1.969353 0.758487 H 1.794185 2.971338 1.139858 C 0.016712 1.815002 0.596852 H 0.751368 2.281606 1.199581 O 2.557962 1.030805 1.354290 O 2.165595 0.980780 1.515370 C 2.886329 1.238722 2.737929 C 3.583935 1.161145 1.642361 C 4.350199 0.939725 2.961790 C 5.220434 1.942140 3.404958 C 4.857661 0.34 6826 2.727405 C 6.574321 1.670622 3.617088 H 4.836612 2.943860 3.588308 C 6.210935 0.615953 2.929523 H 4.185363 1.129265 2.388831 C 7.072590 0.389885 3.376885 H 7.236762 2.459211 3.964954 H 6.593848 1.615967 2.742836 H 8.125920 0.174971 3.537972 C 4.157713 0.034500 2.360490 C 3.979867 1.320308 1.826999 C 4.881072 0.117735 3.547449 C 4.521150 2.429449 2.476488 H 3.409307 1.442675 0.910608 C 5.430965 0.992973 4.193119 H 5.014450 1.110602 3.971540 C 5.250680 2.269099 3.658790 H 4.378309 3.421570 2.055552 H 5.993387 0.859893 5.113762 H 5.675495 3.135278 4.159914 H 2.25 1505 0.587855 3.352714 H 2.674700 2.281703 3.016273 H 3.788326 2.086258 2.204133 H 4.022354 1.258558 0.642399 C 0.271373 0.775392 4.897911 O 0.134746 1.679006 5.586272 C 0.039427 0.685343 5.162520 H 0.874098 1.256517 5.365638 H 0.548024 1.153976 4.314033 H 0.688957 0.732891 6.036643 5E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.15361621000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.181 324890 0 a.u Ru 1.661151 0.030582 0.666544 O 1.927057 2.411421 1.629809 O 1.436371 0.599652 2.744640 N 3.507943 0.471795 1.496508 N 1.538476 0.579447 2.469404 C 2.171711 0.359379 1.273833 C 3.86 8460 0.718007 2.896323 C 4.455611 0.044459 0.501716 C 4.879423 1.495334 0.858788 C 5.818968 2.055215 0.227752 C 7.068545 1.159220 0.340992 C 6.639163 0.274056 0.716473 C 5.724082 0.837138 0. 393568 C 5.879682 0.247446 2.060185 C 4.615840 0.649429 1.935755 C 3.723652 0.040655 0.846498 C 5.067162 2.080585 1.570916 C 0.213111 0.153631 2.842258 C 0.015251 1.226985 3.058166 C 1.289101 1.639399 3.446536 C 1.072841 2.256171 2.850358 C 2.491753 0.845830 3.572294 C 0.798504 1.093750 3.096425 C 2.337574 0.730705 3.643711 C 2.063814 0.626331 3.483061 C 0.589598 2.586267 2.96936 5 C 3.715828 1.220947 4.017581 H 3.519779 1.025343 1.125732 H 4.465887 1.630566 2.991940 H 4.456469 0.113090 3.302558 H 3.981128 2.119147 0.941553 H 5.386341 1.509607 1.833863 H 6.117881 3. 074192 0.050375 H 7.623357 1.151766 0.608218 H 7.748209 1.559010 1.105076 H 7.525499 0.915705 0.805476 H 5.431448 1.871707 0.167584 H 6.267138 0.853024 1.350061 H 5.595363 1.266866 2.356057 H 6.534596 0.143201 2.850950 H 4.082960 0.653201 2.891855 H 4.200394 2.743630 1.512124 H 5.724568 2.467358 2.361511 H 1.473600 2.701830 3.590003 H 1.985729 2.013544 3.407621 H 1.352518 2.341582 1.793920 H 0.734360 3.241114 3.184664 H 2.344915 0.120890 4.379414 H 2.321379 1.845268 3.988153 H 2.854747 1.352512 3.658002 H 1.085185 3.111989 3.792729 H 1.023374 2.971775 2.038631 H 0.468708 2.859417 2.982991 H 4.139306 1.836335 3.214394 H 4.402161 0.388462 4.199307 H 3.687912 1.841583 4.921740 N 1.669393 1.885192 2.749040 O 1.624474 2.509642 3.798055 C 0.630428 1.66 1673 1.073121 H 0.653335 1.812763 2.159162 C 0.802248 2.970391 0.346127 H 0.953410 2.822855 0.725062 H 1.661413 3.512002 0.756842 O 0.411157 3.750234 0.541692

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276 C 0.157145 0.787460 0.317400 H 0.408187 1.118026 0.686272 C 1.153991 1.300510 1.365358 H 0.765699 1.903783 2.194328 C 1.485556 0.176772 1.760220 H 1.120405 0.427123 2.767491 C 0.539029 0.756189 0.651904 H 1.067073 1.166301 0.211202 O 2.176277 2.000712 0.694179 O 2.834189 0.515643 1.599893 C 3.136231 2.602726 1.554430 C 3.110967 1.859843 2.018360 C 4.083467 3.450808 0.736764 C 5.423764 3.575034 1.118851 C 3.63 2246 4.155541 0.386634 C 6.297964 4.393730 0.401063 H 5.788059 3.024002 1.983360 C 4.506685 4.966581 1.111247 H 2.595056 4.054361 0.689716 C 5.841843 5.091348 0.718432 H 7.336194 4.478484 0. 711620 H 4.143945 5.507791 1.981820 H 6.521277 5.725319 1.282203 C 4.496570 2.267831 1.582062 C 5.592486 1.413664 1.761050 C 4.701653 3.532961 1.017564 C 6.872134 1.817108 1.381066 H 5.436102 0.427427 2.188543 C 5.985782 3.940505 0.647225 H 3.854407 4.198900 0.865508 C 7.073066 3.084193 0.826208 H 7.714328 1.143635 1.519170 H 6.132574 4.925643 0.211767 H 8.071490 3.399217 0.53345 2 H 3.016275 1.909676 3.117167 H 2.373096 2.549945 1.593524 H 3.691985 1.833838 2.105402 H 2.611704 3.229915 2.297498 C 0.499278 5.073021 0.247201 O 1.569175 5.623846 0.371050 C 0.758075 5.789011 0.207015 H 1.213785 5.296771 1.072998 H 1.506620 5.807448 0.593561 H 0.491424 6.813362 0.467993 6E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.15871681000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution : 2493.18750595000 a.u Ru 1.724331 0.198446 0.471367 O 2.697870 1.426593 2.882592 O 1.685575 0.488370 2.516979 N 3.292477 0.228120 1.950486 N 1.347139 0.939471 2.658347 C 2.043732 0.574990 1.54015 7 C 3.438614 0.171928 3.409598 C 4.177063 0.495304 1.029179 C 3.970160 2.029337 1.164033 C 4.837145 2.771583 0.129036 C 6.320945 2.433800 0.379672 C 6.532375 0.910866 0.244421 C 5.667051 0. 174566 1.291655 C 6.123363 0.465133 1.173284 C 4.629520 0.800099 1.424976 C 3.786382 0.035598 0.389473 C 4.425937 2.322416 1.286676 C 0.047418 1.543864 2.760255 C 1.078484 0.743579 3.040799 C 2.329662 1.365232 3.133138 C 0.991916 0.746354 3.291730 C 2.189864 0.927761 3.874449 C 0.068692 2.949498 2.696785 C 2.488759 2.745872 2.992865 C 1.340254 3.521284 2.801829 C 1.140236 3.84780 0 2.542919 C 3.861095 3.374402 3.035987 H 3.998202 1.048485 0.477128 H 4.367817 0.644374 3.738514 H 3.441861 0.870004 3.756115 H 2.908852 2.263937 1.011614 H 4.238017 2.356611 2.178655 H 4. 680331 3.852655 0.239399 H 6.624413 2.772986 1.380492 H 6.955253 2.964073 0.342968 H 7.587878 0.666735 0.422016 H 5.825035 0.910403 1.229293 H 5.961371 0.492516 2.302778 H 6.291297 0.613110 1.298100 H 6.749347 0.973691 1.919477 H 4.369803 0.480186 2.435363 H 3.377604 2.577930 1.482550 H 5.031337 2.849155 2.036781 H 3.204308 0.746288 3.323404 H 1.396962 0.984389 4.282996 H 0.035193 1.114829 3.250592 H 1.580993 1.314168 2.562446 H 1.664682 0.435827 4.698094 H 2.421279 1.955003 4.181250 H 1.435967 4.602026 2.723857 H 1.603369 4.057042 3.516632 H 0.853279 4.812783 2.113698 H 1.909882 3.406593 1.902903 H 4.391479 3.212466 2.088680 H 3.803111 4.454387 3.204302 H 4.477032 2.937135 3.829882 N 2.250066 0.351760 3.351827 O 2.311378 0.046307 4.536641 C 0.27 6974 1.491921 1.193571 H 0.323414 1.440988 2.281034

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277 C 0.136261 2.920830 0.738146 H 0.060235 2.998190 0.341273 H 0.975742 3.527336 1.088417 O 1.123011 3.461532 1.220222 C 0.225533 0.968059 0. 068476 H 0.020510 1.215351 0.962824 C 0.558860 1.821063 1.068634 H 0.043749 2.304232 1.847826 C 1.322276 0.563510 1.587019 H 1.083303 0.338913 2.635585 C 0.598111 0.430098 0.611411 H 1.218000 0.776808 0.216210 O 1.323677 2.763416 0.353791 O 2.707659 0.611629 1.374328 C 2.039007 3.678753 1.185309 C 3.381776 0.499082 1.988710 C 2.997074 4.471044 0.329646 C 3.035273 5.867153 0.39122 5 C 3.885720 3.802967 0.525303 C 3.950194 6.589381 0.379718 H 2.343899 6.394421 1.044943 C 4.793864 4.522308 1.300950 H 3.852702 2.718493 0.575898 C 4.830497 5.918282 1.228733 H 3.968586 7. 674563 0.320908 H 5.477239 3.994409 1.961499 H 5.540435 6.477871 1.832276 C 4.721925 0.739765 1.338116 C 5.550645 0.320462 0.950268 C 5.160309 2.057137 1.148721 C 6.796755 0.066451 0.375165 H 5.215004 1.343511 1.091781 C 6.412620 2.309178 0.582908 H 4.519355 2.882082 1.453765 C 7.232201 1.248331 0.191349 H 7.430685 0.896938 0.074578 H 6.745685 3.335111 0.447560 H 8.205125 1.444056 0.252219 H 2.591968 3.118003 1.951346 H 1.333174 4.349013 1.700685 H 3.497734 0.282947 3.063515 H 2.775924 1.407531 1.899904 C 1.263286 4.007196 2.459123 O 2.385696 4.215571 2.862820 C 0.014427 4.365791 3.242129 H 0.561952 5.135725 2.715300 H 0.649496 3.508584 3.395348 H 0.327437 4.758173 4.209894 7E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.15615611000 a.u. M06/SDD/6 311++G(d,p) SCF e nergy in solution: 2493.18867258000 a.u Ru 1.705952 0.334509 0.683703 O 1.823277 1.794233 3.200570 O 1.808096 0.378007 2.795140 N 3.419226 0.529998 1.694186 N 1.460526 1.145620 2.440688 C 2.129108 0.721316 1.334006 C 3.656747 0.659748 3.136629 C 4.356886 0.113598 0.770862 C 4.461141 1.631386 1.077445 C 5.358769 2.319237 0.032454 C 6.770535 1.703466 0.104420 C 6.684673 0.190403 0.186068 C 5.779023 0.490200 0.867802 C 6.094547 0.014102 1.595621 C 4.669032 0.594234 1.668519 C 3.784490 0.133410 0.635976 C 4.752829 2.104219 1.368384 C 0.098347 1.575889 2.575527 C 0.880841 0.644 321 2.970046 C 2.190856 1.102123 3.159092 C 0.551153 0.809423 3.207036 C 2.348901 1.303911 3.614095 C 0.207441 2.946702 2.457124 C 2.538868 2.446990 3.005203 C 1.527667 3.355851 2.673309 C 0.853779 3.970324 2.118383 C 3.967034 2.906495 3.181339 H 3.903842 1.228317 0.835533 H 4.534586 1.278312 3.341821 H 3.820920 0.326966 3.587927 H 3.462274 2.077754 1.076408 H 4.879135 1.778638 2.083799 H 5.412458 3.392877 0.257096 H 7.210733 1.878164 1.096758 H 7.431070 2.186219 0.627982 H 7.686821 0.254804 0.131511 H 5.731832 1.573430 0.692215 H 6.203605 0.338311 1.871376 H 6.058 229 1.083915 1.843037 H 6.744329 0.463180 2.342261 H 4.284139 0.437064 2.678068 H 3.754918 2.552086 1.432958 H 5.375651 2.599354 2.125599 H 2.955003 0.382666 3.444357 H 1.324388 1.279462 3.822073 H 0.410356 0.929849 3.718146 H 0.501592 1.370161 2.267996 H 1.916352 0.809553 4.488539 H 2.473207 2.366818 3.852593 H 1.771522 4.412985 2.584536 H 1.484079 4.205044 2.986106 H 0.39708 2 4.911244 1.795982 H 1.519623 3.623863 1.321108 H 4.504434 2.890813 2.224120 H 4.015510 3.931168 3.565212 H 4.514045 2.256836 3.872264

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278 N 2.075173 0.646151 3.594797 O 2.531512 0.377066 4.702 274 C 0.400804 1.565181 1.532669 H 0.076873 1.512867 2.568058 C 0.743802 2.939682 1.033795 H 0.787999 2.977895 0.055627 H 0.040704 3.692862 1.404994 O 2.073303 3.195176 1.565762 C 1.112232 1.363226 0.316788 H 1.654616 2.054599 0.340238 C 0.176558 1.973961 0.825184 H 0.059071 2.831609 1.473140 C 0.956636 0.904027 1.607221 H 0.517679 0.845588 2.609840 C 0.826455 0.433372 0.910499 H 1.286359 0.492768 0.074404 O 0.885504 2.414399 0.333441 O 2.334117 1.264911 1.690510 C 1.667967 3.605821 0.153339 C 3.033905 0.578645 2.742782 C 2.656313 3.700952 1.287503 C 2.497273 4.639 768 2.311669 C 3.747031 2.819456 1.332417 C 3.413839 4.707235 3.364420 H 1.651928 5.323962 2.284449 C 4.661219 2.883370 2.383361 H 3.870319 2.090835 0.535879 C 4.496797 3.827965 3.401987 H 3.281586 5.444805 4.151829 H 5.508636 2.202812 2.403348 H 5.213307 3.880422 4.217823 C 4.516591 0.622733 2.472260 C 5.218628 1.833778 2.547208 C 5.209655 0.547354 2.135805 C 6.587913 1.877306 2.286318 H 4.686761 2.744512 2.812489 C 6.583041 0.505726 1.882553 H 4.677454 1.494804 2.077666 C 7.273570 0.705152 1.954860 H 7.121627 2.822211 2.348052 H 7.111145 1.421601 1.630619 H 8.342332 0.736754 1.758785 C 2.681285 4.405847 1.474038 O 3.841500 4.493145 1.802641 C 1.858750 5.582706 0.985478 H 1.440029 5.393125 0.008677 H 1.021582 5.782715 1.664186 H 2.505290 6.459719 0.946718 H 2.191152 3.546965 0.806233 H 1.004473 4.483915 0.139165 H 2.704050 0.464924 2.797005 H 2.790046 1.062377 3.701777 8E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.17822482000 a.u. M06/SDD/6 311++ G(d,p) SCF energy in solution: 2493.19593519000 a.u Ru 1.622862 0.226096 0.587313 O 2.236886 2.423301 1.049854 O 1.372284 1.159905 2.589617 N 3.706842 0.729033 1.191679 N 2.139572 0.080694 2.493179 C 2. 479254 0.151636 1.199165 C 4.178026 1.096639 2.529551 C 4.231140 1.252630 0.071425 C 3.952082 2.773137 0.196856 C 4.362495 3.273586 1.593380 C 5.873553 3.036117 1.787332 C 6.173311 1.529730 1.650331 C 5.756972 1.043378 0.237532 C 5.388396 0.774954 2.746819 C 3.862725 0.989569 2.544529 C 3.525513 0.414025 1.156144 C 3.554637 2.495387 2.652520 C 1.031747 0.852951 2.981570 C 0.1014 28 0.183494 3.480294 C 1.129395 0.951488 4.041187 C 0.229945 1.320440 3.419000 C 3.225883 0.287952 3.427351 C 1.148338 2.255423 3.062430 C 1.050158 2.344198 4.134484 C 0.099761 2.974561 3.64 5024 C 2.361079 2.984476 2.528718 C 2.180499 3.151005 4.730504 H 3.986907 0.586973 1.113969 H 5.227916 0.826157 2.673611 H 4.076136 2.177897 2.694503 H 2.893387 2.977048 0.019314 H 4.518118 3.313287 0.575968 H 4.143698 4.346945 1.671434 H 6.443659 3.610501 1.043342 H 6.190546 3.391259 2.777154 H 7.249274 1.353919 1.779389 H 6.001527 0.018824 0.107953 H 6.318868 1.606174 0.523017 H 5.622578 0.297360 2.718505 H 5.697660 1.142755 3.735470 H 3.312165 0.440018 3.315750 H 2.480856 2.673302 2.510596 H 3.810263 2.855694 3.658616 H 2.009119 0.441378 4.427233 H 1.045522 1.661602 4.063685 H 0.688467 1.823649 3.741389 H 0.452062 1.662237 2.401700 H 2.831757 0.865331 4.268105 H 3.703245 0.614994 3.828199 H 0.185011 4.056924 3.718488 H 3.295328 2.612553 2.965480 H 2.296510 4.052886 2.756147

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279 H 2.452100 2.878217 1.441803 H 2.860184 3.516405 3.949440 H 1.805764 4.028179 5.269052 H 2.776047 2.552025 5.427069 N 1.819700 2.324425 2.260334 O 1.824209 3.25 9073 3.041067 C 0.993815 2.024478 0.750000 H 0.803162 2.266765 1.794900 C 0.989653 3.185142 0.202138 H 1.206844 2.857102 1.220159 H 0.018815 3.687598 0.203077 O 2.045445 4.104597 0.148904 C 0.741350 1.397093 0.488013 H 1.101217 2.310423 0.005974 C 0.694773 1.640658 0.921272 H 0.701108 2.387981 1.733532 C 1.399489 0.367455 1.416819 H 0.940282 0.062423 2.369708 C 1.272773 0.754784 0.411211 H 1.517076 0.501387 0.619063 O 1.373018 2.170872 0.222111 O 2.772697 0.703240 1.636136 C 2.262762 3.268833 0.032435 C 3.488604 0.245392 2.430428 C 3.210073 3.398311 1.132811 C 3.09 0239 4.442665 2.055134 C 4.224071 2.445294 1.309155 C 3.970812 4.542337 3.135621 H 2.304874 5.184408 1.925793 C 5.101730 2.540893 2.387762 H 4.316648 1.635407 0.590551 C 4.977254 3.590499 3. 303752 H 3.870255 5.361599 3.842892 H 5.888182 1.800917 2.511886 H 5.665055 3.666882 4.142010 C 4.907676 0.235867 2.605542 C 5.166584 1.471508 3.215527 C 5.985073 0.543670 2.171636 C 6.476252 1.916708 3.387429 H 4.334029 2.084187 3.551866 C 7.299244 0.103570 2.349237 H 5.794821 1.502368 1.694771 C 7.547082 1.127885 2.956078 H 6.663927 2.876725 3.861287 H 8.126180 0.721858 2.010134 H 8.568387 1.473143 3.093587 H 2.819380 3.072710 0.954365 H 1.680247 4.193821 0.162760 H 2.987430 0.344330 3.408217 H 3.478801 1.234556 1.953983 C 1.835856 5.233495 0.888121 O 2.7988 98 5.896862 1.189523 C 0.415494 5.612884 1.266166 H 0.190498 5.817153 0.375700 H 0.098505 4.835435 1.841203 H 0.470467 6.520344 1.867984 9E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.18425936000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.19755243000 a.u Ru 1.669873 0.390325 1.015108 O 1.840625 1.597829 1.888362 O 0.457584 0.222978 2.845928 N 3.627453 1.839619 0.518383 N 3.506116 0.169649 1 .405663 C 3.015592 0.629251 0.422995 C 4.451081 1.963050 1.725129 C 3.050661 2.955024 0.240358 C 2.043527 3.750782 0.628623 C 1.355562 4.835075 0.224291 C 2.421257 5.799303 0.780806 C 3.423217 5.008875 1.647592 C 4.120085 3.933271 0.778373 C 2.663462 4.340715 2.815303 C 1.596565 3.361196 2.257357 C 2.327292 2.291514 1.431957 C 0.603089 4.156984 1.386758 C 3.326297 1.590031 1.5333 04 C 2.537764 2.079789 2.592164 C 2.433139 3.464550 2.758244 C 1.802409 1.151483 3.530464 C 4.606709 0.490537 2.142776 C 4.004012 2.466646 0.664712 C 3.090436 4.364386 1.912017 C 3.863186 3 .843625 0.870045 C 4.856282 1.965280 0.477895 C 3.002871 5.855565 2.144845 H 3.123521 1.855786 2.088112 H 5.409014 2.447359 1.515590 H 3.927968 2.549356 2.492701 H 1.298665 3.062679 1.043003 H 2.569574 4.217822 1.473277 H 0.645978 5.389754 0.403772 H 2.945437 6.303039 0.043559 H 1.944045 6.584721 1.382202 H 4.185854 5.690245 2.046394 H 4.860803 3.379257 1.370274 H 4.659062 4.4183 07 0.048930 H 3.364974 3.801905 3.466770 H 2.182779 5.111802 3.433353 H 1.064697 2.884398 3.090094 H 0.172343 3.491179 0.992559 H 0.096404 4.914918 1.999852 H 1.827298 3.848678 3.576322 H 1.299460 1.720206 4.318088 H 2.473095 0.434064 4.018153 H 1.041353 0.567705 3.000843 H 4.506115 0.335291 3.219918

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280 H 5.571007 0.071542 1.825769 H 4.383725 4.525429 0.200757 H 5.475128 1.107189 0.193955 H 5.523186 2.756217 0.834305 H 4.229576 1.654816 1.321482 H 3.088367 6.415514 1.207374 H 3.812351 6.200620 2.801984 H 2.057701 6.134165 2.622564 N 0.944707 1.405906 2.817418 O 0.60 2864 2.294717 3.569204 C 1.229025 2.783252 0.243680 H 0.983182 2.861088 1.302835 C 0.942969 3.999143 0.586422 H 1.327992 3.873721 1.602295 H 0.135909 4.175909 0.656498 O 1.612315 5.170654 0. 076763 C 0.303255 0.635316 0.174094 H 0.480270 0.619399 1.256878 C 1.185570 0.845118 0.090380 H 1.332749 1.630655 0.844769 C 1.918594 0.412962 0.624885 H 1.540467 0.607566 1.637262 C 1.713704 1.633158 0.233527 H 1.986991 1.530964 1.283481 O 1.753513 1.252702 1.156033 O 3.303372 0.054330 0.697657 C 2.693260 2.333006 1.090505 C 4.088190 0.931145 1.508047 C 3.507036 2.339143 2.36032 3 C 3.342159 3.335533 3.326932 C 4.444821 1.320739 2.584617 C 4.104023 3.324354 4.498461 H 2.614725 4.127489 3.160953 C 5.203343 1.304943 3.753649 H 4.572940 0.549176 1.830117 C 5.035348 2. 308131 4.713707 H 3.968656 4.107181 5.240464 H 5.931083 0.513874 3.915590 H 5.630187 2.297243 5.623464 C 5.500268 0.402470 1.567880 C 5.754911 0.873042 2.091546 C 6.574669 1.171727 1.109612 C 7.056603 1.367471 2.153294 H 4.924211 1.477541 2.446678 C 7.881704 0.682202 1.176685 H 6.387284 2.161091 0.698649 C 8.124781 0.588989 1.697179 H 7.240596 2.358380 2.560414 H 8.706571 1.292803 0.818952 H 9.140177 0.973158 1.748432 H 3.349428 2.194445 0.225372 H 2.155985 3.287385 0.973585 H 3.649001 0.977422 2.518654 H 4.076421 1.950375 1.099235 C 1.061826 5.973815 0.877614 O 1.710127 6.913030 1.273278 C 0.337864 5.664829 1.381650 H 1.075246 5.704394 0.572048 H 0.409596 4.673598 1.841960 H 0.589669 6.419664 2.127098 10E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2494.1864 5034000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2493.19756091000 a.u Ru 2.041456 0.065664 0.992545 O 2.151359 1.933989 2.110050 O 0.895653 0.360113 2.928241 N 3.980974 1.051302 0.818734 N 3.668084 1 .036175 1.439794 C 3.296332 0.089653 0.539882 C 4.730069 0.964447 2.076528 C 3.508673 2.289610 0.188218 C 2.496345 3.021732 1.106450 C 1.917145 4.249810 0.378352 C 3.062830 5.210984 0.005114 C 4.065158 4.481258 0.913045 C 4.656451 3.262005 0.163319 C 3.328652 4.021975 2.191364 C 2.183227 3.042300 1.817812 C 2.819628 1.833725 1.115702 C 1.186876 3.768979 0.891647 C 3.335144 2.4322 66 1.386840 C 2.423734 2.944301 2.331259 C 2.127740 4.309476 2.297877 C 1.779789 2.055115 3.369312 C 4.759705 0.556273 2.314185 C 3.961935 3.274127 0.449927 C 2.712424 5.170283 1.362515 C 3 .630740 4.633841 0.457049 C 4.962567 2.754903 0.556494 C 2.348202 6.636194 1.323575 H 3.626076 1.446959 1.789976 H 5.730237 1.396928 1.983925 H 4.199065 1.490885 2.881161 H 1.690114 2.332376 1.378846 H 2.995934 3.336329 2.033539 H 1.206613 4.757399 1.042949 H 3.569114 5.568038 0.913249 H 2.663133 6.096723 0.506691 H 4.883270 5.161251 1.184079 H 5.397816 2.746204 0.788410 H 5.175065 3.603556 0.744836 H 4.030376 3.533696 2.881504 H 2.921440 4.897113 2.716872 H 1.673299 2.709909 2.730755 H 0.365834 3.100482 0.610618 H 0.748071 4.626313 1.420931 H 1.423719 4.711195 3.023825

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281 H 1.016131 2.603813 3.929035 H 2.509304 1.680569 4.099266 H 1.306257 1.178061 2.915994 H 4.580455 0.831924 3.356532 H 5.712845 1.003319 2.001216 H 4.108912 5.289869 0.267241 H 5.602 020 1.968661 0.142377 H 5.609276 3.565772 0.906123 H 4.451445 2.339062 1.432220 H 1.471822 6.807291 0.684528 H 3.166615 7.241880 0.920478 H 2.102631 7.016329 2.321137 N 1.344950 1.553215 3.0 65517 O 1.055420 2.279085 3.989635 C 3.211602 1.753773 1.306002 H 4.050115 1.638997 0.623366 C 3.503262 2.212117 2.703902 H 2.575120 2.405003 3.248504 H 4.099788 3.130452 2.717969 O 4.165429 1.180458 3.477503 C 0.592857 0.162650 0.093521 H 0.633947 0.131170 1.190387 C 0.819162 0.387055 0.411931 H 0.793650 0.800247 1.429301 C 1.615746 0.964274 0.486521 H 0.942789 1.700737 0.957917 C 1.979727 1.454944 0.888659 H 1.140456 1.549917 1.576907 O 1.414375 1.321263 0.485416 O 2.796753 0.846769 1.267547 C 2.502043 2.087005 0.055901 C 2.608447 1.015547 2.674655 C 3.151944 2.8 72552 1.055958 C 3.254999 4.266014 0.992974 C 3.697206 2.201254 2.159644 C 3.901900 4.977408 2.007400 H 2.830893 4.798337 0.143896 C 4.343475 2.906110 3.173647 H 3.608865 1.121702 2.227594 C 4.448548 4.298633 3.097483 H 3.977040 6.060250 1.944286 H 4.775741 2.357474 4.005721 H 4.956303 4.851068 3.884230 C 3.960304 1.074303 3.343209 C 4.272816 0.219175 4.404334 C 4.918269 2.005685 2.918693 C 5.516157 0.293828 5.037462 H 3.538338 0.510219 4.738217 C 6.162203 2.077864 3.543084 H 4.682307 2.670542 2.092099 C 6.464076 1.222157 4.606778 H 5.743956 0.377034 5.861572 H 6.896993 2.803716 3.204078 H 7.433222 1.280045 5.095217 H 3.227115 1.410081 0.521702 H 2.122243 2.765224 0.836385 H 2.009672 0.196826 3.094597 H 2.046428 1.947416 2.851875 C 5.516463 1.068736 3.567640 O 5.976517 0.131439 4.177375 C 6.383286 2.134968 2.920345 H 6.228670 3.112256 3.392128 H 6.171076 2.242600 1.851545 H 7.424575 1.840388 3.052213 14 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93726084000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.86611049000 a.u Ru 0.481444 1.077252 0.694950 O 1.122876 1.170916 3.055949 O 0.032409 0.452853 2.191883 N 0.265991 3.644361 0.422439 N 1.682472 3.233773 1.331741 C 0.748494 2.748376 0.450195 C 0.151759 4.705052 1.425591 C 1.471647 3.372626 0.363281 C 2.614452 2.822512 0.524289 C 3.831127 2.468957 0.354503 C 4.320681 3.728628 1.095175 C 3.181308 4.274515 1.980101 C 1.980024 4.647885 1.081950 C 2.768221 3.193815 3.003822 C 2.260585 1.930244 2.258535 C 1.030332 2.349958 1.427400 C 3.408193 1.396403 1.377614 C 3.062800 2.859183 1.453094 C 3.503899 2.273010 2.655704 C 4.862400 1.968926 2.792187 C 2.544350 1.969473 3.784152 C 1.317420 4.576765 1.839848 C 3.975788 3.184852 0.428788 C 5.787534 2.24 1755 1.780067 C 5.323708 2.858495 0.613363 C 3.537419 3.886582 0.838277 C 7.242287 1.865653 1.934032 H 0.356825 2.893304 2.113503 H 0.389260 5.685507 1.004441 H 0.835606 4.516357 2.264038 H 2.272395 1.932673 1.062733 H 2.899046 3.574021 1.274650 H 4.631738 2.077406 0.286353 H 4.641662 4.494076 0.374342 H 5.194341 3.486676 1.715440 H 3.521784 5.174128 2.509576 H 1.166848 5.078094 1.682065 H 2.293302 5.412855 0.355986 H 1.983853 3.578383 3.669401 H 3.629247 2.939022 3.637967

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282 H 1.981368 1.167897 2.993797 H 3.100685 0.487088 0.855276 H 4.262523 1.121622 2.011509 H 5.20 4776 1.503802 3.714041 H 2.230577 2.882440 4.307149 H 1.631456 1.482212 3.425265 H 3.013622 1.316346 4.525772 H 1.467148 4.637897 2.920818 H 1.949286 5.338689 1.365044 H 6.031995 3.100747 0. 176168 H 3.060994 4.851425 0.625402 H 4.398316 4.080880 1.484562 H 2.813357 3.297442 1.412026 H 7.547759 1.866491 2.985529 H 7.430700 0.858544 1.539867 H 7.894786 2.555554 1.388537 C 0.621958 3.829637 2.358984 H 0.945741 3.955788 3.391323 C 0.861929 5.034789 1.488631 H 0.002025 5.710571 1.539663 H 0.997900 4.767811 0.437139 N 0.471349 0.093758 3.251783 O 0.327584 0.416454 4.35328 6 O 1.962659 5.816502 1.980256 C 0.335749 0.182880 0.713559 H 0.213654 0.440089 1.776659 C 1.265263 1.017237 0.578842 H 1.790240 0.980035 0.381763 C 0.517926 2.387113 0.615795 H 0.310998 2.314083 0.104451 C 0.014916 2.692892 1.999374 H 0.148127 1.929085 2.754878 O 2.191505 0.857653 1.654636 O 1.349854 3.475624 0.199891 C 3.431064 1.573034 1.538891 C 1.449809 3.706288 1.216919 C 4.382041 1.053407 2.588719 C 4.044895 1.125346 3.947773 C 5.617991 0.505247 2.228486 C 4.924059 0.657070 4.923068 H 3.086181 1.548398 4.236031 C 6.505172 0.042240 3.203921 H 5.890046 0.445 348 1.177040 C 6.159005 0.115644 4.553329 H 4.649946 0.718768 5.973153 H 7.463158 0.377374 2.907946 H 6.846369 0.244950 5.314101 C 2.781401 3.297838 1.812767 C 3.972097 3.850323 1.317796 C 2.842607 2.403786 2.888762 C 5.201458 3.503947 1.876787 H 3.931028 4.551334 0.487565 C 4.074704 2.064708 3.456798 H 1.927526 1.968100 3.281161 C 5.255273 2.609254 2.950544 H 6.116900 3.937920 1.482778 H 4.107241 1.373719 4.295082 H 6.212722 2.345008 3.391956 H 3.853247 1.434205 0.535398 H 3.246995 2.646045 1.670903 H 1.309334 4.787850 1.343701 H 0.634294 3.195270 1.742649 C 3.260 985 5.558168 1.636255 O 4.128142 6.200422 2.176100 C 3.530438 4.503118 0.582099 H 3.134641 3.526488 0.879101 H 3.066433 4.773944 0.373589 H 4.606316 4.419710 0.430583 C 2.291854 0.241157 0.4 99421 C 2.762244 0.110279 0.733712 H 2.447102 0.385928 1.364751 H 1.967556 1.256733 0.698134 H 3.306543 1.042484 0.841069 C 2.981972 0.913990 1.818132 H 3.093629 0.426100 2.787783 H 2.150285 1.623468 1.866785 O 4.188405 1.634113 1.468971 C 4.817044 2.446859 2.365687 O 5.732636 3.130748 1.973460 C 4.342959 2.428885 3.806423 H 4.505613 1.444260 4.260013 H 3.274102 2.652299 3.893169 H 4.915860 3.173869 4.358981 15 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.96124459000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.88742652000 a.u Ru 0.048267 0.930575 0.930936 O 0.144749 0.580204 3.855 674 O 0.722241 0.679512 2.155366 N 0.465404 3.444439 0.386526 N 1.497454 2.867113 1.166266 C 0.512465 2.511946 0.291326 C 0.288024 4.372801 1.506045 C 1.720790 3.221599 0.330777 C 2.746736 2.470157 0.558501 C 4.016225 2.153685 0.255628 C 4.638907 3.470935 0.760963 C 3.619382 4.217019 1.646991 C 2.357342 4.544158 0.817109 C 3.238622 3.323775 2.844463 C 2.608131 1.996891 2.341223 C 1.337315 2.358649 1.551671 C 3.633035 1.262419 1.453213 C 2.875066 2.450115 1.157677 C 3.362447 1.612661 2.176206 C 4.716410 1.252407 2.153689 C 2.488584 1.091042 3.294978

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283 C 1.184676 4.133400 1.869609 C 3.740943 2.970906 0.169702 C 5.592583 1.727401 1.175117 C 5.085192 2.594176 0.199124 C 3.238742 3.885457 0.925712 C 7.047805 1.322911 1.185305 H 0.658427 2.938941 2.201414 H 0.491434 5.405606 1.209722 H 0.963118 4.113048 2.332288 H 2.298461 1.544559 0.941248 H 3.005595 3.088555 1.429780 H 4.730334 1.627360 0.389326 H 4.937079 4.100367 0.089478 H 5.550475 3.26 1564 1.336922 H 4.058783 5.155771 2.009008 H 1.630918 5.101763 1.423633 H 2.629902 5.179850 0.038077 H 2.533520 3.847590 3.503879 H 4.132661 3.103331 3.444182 H 2.349362 1.387568 3.208980 H 3.213473 0.310605 1.105944 H 4.527416 1.019112 2.043057 H 5.086593 0.555447 2.900175 H 2.832247 1.476520 4.263307 H 1.441732 1.376751 3.169745 H 2.543170 0.001837 3.349011 H 1.351503 4.022483 2.944748 H 1.838511 4.935371 1.505644 H 5.753650 2.979894 0.567861 H 2.752411 4.784864 0.529071 H 4.067944 4.213495 1.559549 H 2.503459 3.385413 1.567245 H 7.606055 1.881071 1.948941 H 7.15 1519 0.258550 1.417469 H 7.524334 1.520448 0.219501 C 1.663092 2.997251 2.950609 H 1.909773 2.916314 4.008615 C 2.840052 3.361237 2.092006 H 3.188237 4.370910 2.349070 H 2.613071 3.339422 1. 022774 N 0.669341 0.476965 3.448774 O 1.123721 1.347232 4.192231 O 3.884563 2.411503 2.402731 C 0.201754 0.372940 0.590719 H 0.388131 0.056767 1.575179 C 0.819358 1.508560 0.730004 H 1.320995 1.695730 0.225397 C 0.181017 2.859824 1.184471 H 0.596695 3.118838 0.456272 C 0.397277 2.784651 2.574127 H 0.333845 2.545702 3.342747 O 1.763715 1.019698 1.686901 O 1.138295 3.924841 1.21505 9 C 3.079199 1.569713 1.609857 C 1.317775 4.690268 0.012706 C 3.997784 0.829109 2.554868 C 3.518051 0.220722 3.721248 C 5.373756 0.792435 2.290954 C 4.396464 0.414123 4.601973 H 2.453640 0.243955 3.930892 C 6.253292 0.164444 3.174379 H 5.757385 1.262222 1.387526 C 5.766352 0.443714 4.333557 H 4.008869 0.884132 5.502613 H 7.317491 0.144882 2.953585 H 6.448850 0.937068 5.020612 C 2.582814 4.345266 0.744898 C 3.826232 4.773092 0.256185 C 2.542855 3.593991 1.925466 C 5.005032 4.442838 0.924548 H 3.867559 5.366343 0.654955 C 3.721426 3.263007 2.599143 H 1.597563 3.242 710 2.327906 C 4.954341 3.685216 2.099386 H 5.961553 4.783018 0.535661 H 3.659695 2.674165 3.509601 H 5.872395 3.432271 2.623695 H 3.457935 1.496941 0.580224 H 3.052065 2.635648 1.864084 H 1.356298 5.736456 0.339741 H 0.440711 4.575661 0.639495 C 5.140381 2.513867 1.877398 O 5.991579 1.770889 2.312726 C 5.391483 3.497850 0.756717 H 5.059134 3.072657 0.200574 H 4.885897 4.457026 0.897583 H 6.467929 3.661469 0.689101 C 1.555230 0.668737 0.167181 C 1.949574 0.370310 1.289266 H 2.353580 0.635442 0.577557 H 1.506968 1.649529 0.640922 H 2.721122 1.053473 0.944149 C 2.398 025 0.298568 2.571945 H 2.639078 0.443867 3.338393 H 1.655584 0.993123 2.962455 O 3.589218 1.054893 2.210075 C 4.212989 1.875587 3.090710 O 5.059066 2.634996 2.670580 C 3.825075 1.780969 4.5 51991 H 3.950508 0.759559 4.927696 H 2.775159 2.054945 4.704679 H 4.459938 2.460042 5.121466 15 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.95737615000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.879746 73000 a.u Ru 0.755405 1.092845 0.984371 O 2.464589 0.735917 2.192551

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284 O 0.370532 0.205492 2.633796 N 1.750047 3.385908 0.471702 N 2.897350 1.712138 1.298697 C 1.954440 2.052412 0.367973 C 2.407939 4.005514 1.624793 C 0.690333 4.012678 0.314319 C 0.601095 4.160398 0.531063 C 1.735139 4.741145 0.331828 C 1.311434 6.114537 0.889260 C 0.037131 5.950287 1.743808 C 1.101751 5.404175 0.852089 C 0.322070 4.972386 2.904789 C 0.737951 3.585007 2.340597 C 0.450192 3.068596 1.508434 C 2.011354 3.763279 1.486755 C 3.781736 0.573633 1.292099 C 3.617522 0.460112 2.231163 C 4.53 4683 1.520500 2.224925 C 2.505695 0.466485 3.256104 C 3.355903 2.885908 2.080606 C 4.882874 0.576678 0.405013 C 5.622851 1.555540 1.349527 C 5.779410 0.492208 0.452413 C 5.096352 1.687121 0. 600563 C 6.607933 2.699336 1.385070 H 1.357863 3.075086 2.151721 H 2.934614 4.921190 1.340152 H 1.671126 4.261247 2.396413 H 0.891031 3.179866 0.929595 H 0.404458 4.817511 1.389895 H 2.634234 4.848748 0.287671 H 1.127121 6.821038 0.067281 H 2.119866 6.538413 1.499802 H 0.266713 6.924400 2.148754 H 2.035580 5.315508 1.423710 H 1.286891 6.103540 0.023925 H 0.565660 4.872445 3.54479 5 H 1.127816 5.370938 3.536453 H 0.939574 2.899500 3.169268 H 2.336186 2.794452 1.100150 H 2.823702 4.142721 2.121504 H 4.381987 2.350267 2.909921 H 2.920795 0.525077 4.269694 H 1.881024 0. 427632 3.195450 H 1.860209 1.342558 3.125178 H 3.287453 2.674845 3.151947 H 4.403663 3.106400 1.847781 H 6.622700 0.498101 0.234869 H 5.242398 2.663141 0.121536 H 5.984667 1.485812 1.206460 H 4.242954 1.793139 1.280155 H 7.208408 2.670790 2.303901 H 6.084921 3.660051 1.366978 H 7.299022 2.656981 0.536866 C 0.187456 3.532978 2.449452 H 0.030439 3.718765 3.500713 C 0.584932 4.41719 7 1.512208 H 0.302889 5.466828 1.672646 H 0.418218 4.176496 0.459168 N 1.644775 0.178391 2.941576 O 1.958181 0.425716 3.969959 O 1.978880 4.246893 1.850581 C 0.160017 0.265936 0.370013 H 0.552653 0.118519 1.375220 C 1.314026 0.657626 0.460796 H 1.835465 0.459127 0.479704 C 1.539251 2.163565 0.765769 H 1.024275 2.741017 0.014113 C 1.071554 2.577403 2.136901 H 1.548717 2.028961 2.946364 O 1.848818 0.184464 1.483276 O 2.945691 2.381546 0.625843 C 3.231687 0.530907 1.345591 C 3.330626 3.743957 0.482361 C 3.566042 1.644293 2.311171 C 2.968810 1.715011 3.576752 C 4.52 7338 2.602606 1.965322 C 3.326520 2.721925 4.474730 H 2.218353 0.979624 3.849350 C 4.892954 3.605542 2.865945 H 4.994736 2.561403 0.983819 C 4.291787 3.669080 4.124444 H 2.853581 2.764269 5. 452939 H 5.642786 4.339225 2.581142 H 4.571867 4.450560 4.826010 C 4.769970 3.809810 0.028151 C 5.644810 4.752387 0.578146 C 5.235015 2.955175 0.980726 C 6.961591 4.851643 0.122958 H 5.295534 5.412583 1.369396 C 6.551965 3.047689 1.429738 H 4.564821 2.211740 1.402210 C 7.418188 3.998182 0.882201 H 7.630294 5.588855 0.559745 H 6.901573 2.377640 2.210718 H 8.443620 4.069946 1.23521 3 H 3.435891 0.846404 0.314452 H 3.853513 0.350803 1.545589 H 3.199311 4.291691 1.427249 H 2.675326 4.225809 0.265027 C 2.959788 4.966642 1.231012 O 4.086527 4.861368 1.660467 C 2.590386 5. 817617 0.037493 H 2.318860 5.194212 0.825434 H 1.745500 6.481795 0.247093 H 3.461049 6.418094 0.228477 C 1.123688 1.146977 0.509628 C 2.107535 0.334070 1.445524

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285 H 1.764727 1.700040 0.182543 H 0.543033 1.826834 1.131803 H 3.081390 0.238067 0.976902 C 2.246980 0.889138 2.859691 H 3.141612 0.470506 3.332823 H 1.373896 0.670761 3.466281 O 2.452313 2.323017 2.752901 C 1.641178 3.217274 3.375860 O 1.634948 4.361110 2.969230 C 0.817928 2.756796 4.561567 H 1.431346 2.199494 5.277858 H 0.011053 2.103939 4.261287 H 0.407739 3.644001 5.045466 15 B3LYP/SDD/6 31G(d) SCF energy i n gas p hase: 2839.95922544000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.88180230000 a.u Ru 0.324468 1.162665 1.029773 O 0.340703 2.033137 2.457523 O 0.909984 0.098940 2.506465 N 0.331651 3.685390 0.342 189 N 2.107146 2.676145 1.137693 C 1.086352 2.565258 0.238757 C 0.684821 4.530703 1.485242 C 0.911460 3.777522 0.423554 C 2.122355 3.273606 0.406479 C 3.395439 3.280910 0.462132 C 3.666025 4.716100 0.957562 C 2.462539 5.212390 1.785725 C 1.197539 5.220770 0.898228 C 2.250649 4.271923 2.991548 C 1.976804 2.825888 2.498014 C 0.696845 2.864399 1.647182 C 3.183341 2.344237 1.668246 C 3.369258 1.982438 1.127828 C 3.661458 1.039280 2.129336 C 4.913088 0.409060 2.108419 C 2.686612 0.688709 3.230873 C 2.056780 3.960441 1.875930 C 4.338564 2.341927 0.164576 C 5.881547 0.718 862 1.150348 C 5.576028 1.695867 0.194872 C 4.061709 3.381851 0.899147 C 7.224707 0.028522 1.161551 H 0.131896 3.277529 2.257468 H 0.726594 5.587386 1.206799 H 0.052939 4.416181 2.290300 H 1.920673 2.261179 0.780076 H 2.262102 3.919944 1.284389 H 4.239864 2.929220 0.143075 H 3.840281 5.386357 0.103985 H 4.576043 4.738138 1.571857 H 2.652645 6.233527 2.141259 H 0.333648 5.603680 1.458433 H 1.354844 5.887855 0.038086 H 1.413221 4.627083 3.608470 H 3.143700 4.280515 3.631764 H 1.833125 2.162146 3.353866 H 3.013926 1.314861 1.332638 H 4.083004 2.329503 2.298384 H 5.124207 0.365585 2.840447 H 3.087979 0.986772 4.207856 H 1.719834 1.179667 3.098978 H 2.520541 0.393214 3.270538 H 2.160277 3.785251 2.950437 H 2.882699 4.607867 1.557496 H 6.321276 1.957195 0.553500 H 3.773295 4.349503 0.471123 H 4.953448 3.546960 1.510923 H 3.248345 3.077655 1.568560 H 7.865279 0.429124 1.958698 H 7.106791 1.043614 1.345177 H 7.753250 0.168180 0.212798 C 1.15 0207 3.144464 2.780786 H 1.400287 3.149358 3.841119 C 2.229303 3.720476 1.909953 H 2.348890 4.790778 2.126741 H 2.023231 3.608830 0.842418 N 1.144709 1.140678 2.825143 O 2.155945 1.387096 3. 481505 O 3.451132 3.031404 2.257101 C 0.257443 0.211699 0.439365 H 0.522502 0.160714 1.429011 C 0.954388 1.133751 0.572887 H 1.485924 1.226011 0.378074 C 0.601828 2.587535 1.012511 H 0.108693 2.993186 0.285265 C 0.041717 2.665430 2.407071 H 0.717925 2.303029 3.177912 O 1.800201 0.483906 1.524773 O 1.795797 3.379078 0.993443 C 3.202570 0.714709 1.375694 C 1.998762 4.114675 0.225491 C 3.968224 0.194953 2.309308 C 3.427983 0.611804 3.532339 C 5.269732 0.592973 1.975835 C 4.173636 1.412065 4.400298 H 2.419672 0.309448 3.795660 C 6.018949 1.386618 2.846294 H 5.7008 28 0.276348 1.028302 C 5.471527 1.801014 4.062314 H 3.740212 1.728999 5.345807 H 7.027275 1.685262 2.571293 H 6.051299 2.422121 4.740064 C 3.466894 4.422150 0.385016 C 4.148498 5.169425 0.58 5918 C 4.166925 3.960374 1.506158 C 5.505929 5.450895 0.437915

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286 H 3.610564 5.521927 1.462377 C 5.525677 4.249621 1.658981 H 3.646488 3.372486 2.259524 C 6.197306 4.993686 0.688136 H 6.025144 6.029454 1.197810 H 6.057601 3.888790 2.535436 H 7.254572 5.217280 0.805780 H 3.503585 0.523069 0.334227 H 3.431559 1.765584 1.586823 H 1.407791 5.043941 0.173679 H 1.640372 3.543020 1.088496 C 4.651486 3.368115 1.703235 O 5.641826 2.824203 2.139734 C 4.677782 4.358617 0.561060 H 4.323209 3.891715 0.368246 H 4.060204 5.241762 0.749734 H 5.712790 4.667490 0.409490 C 1.526055 0.70 4929 0.349589 C 2.070769 0.288473 1.468436 H 2.335649 0.798025 0.377051 H 1.306166 1.649538 0.839348 H 2.973700 0.789250 1.128679 C 2.311423 0.378053 2.811463 H 2.753469 0.333523 3.518973 H 1.395398 0.792127 3.221054 O 3.275820 1.436124 2.562414 C 3.227171 2.635632 3.196454 O 3.888067 3.547240 2.746468 C 2.361677 2.769274 4.431384 H 2.497476 1.928950 5.120220 H 1.303796 2.805657 4.145842 H 2.626533 3.702140 4.930378 16 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93993599000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.85797317000 a.u Ru 1.481558 0.433538 0.921382 O 0.329121 1.412772 2.120514 O 1.320273 0.451665 3.138226 N 1.766785 2.248372 1.304685 N 1.632114 0.287992 2.283989 C 1.649857 0.924482 1.073108 C 1.641536 2.617089 2.718603 C 2.021859 3.179174 0.197644 C 0.748941 3.959521 0.208972 C 1.057182 4.883911 1.406371 C 2.172296 5.877806 1.029446 C 3.440309 5.089958 0.644504 C 3.119107 4.206593 0.581344 C 3.890084 4.216788 1.837013 C 2.769365 3.204 453 2.202677 C 2.559858 2.301471 0.961396 C 1.520434 4.025125 2.599255 C 2.010041 1.075848 2.543368 C 1.071892 1.975992 3.086698 C 1.463136 3.302446 3.295405 C 0.310670 1.534906 3.505382 C 1.704961 1.244885 3.412320 C 3.355729 1.465582 2.367721 C 2.762755 3.745859 3.034901 C 3.699070 2.801684 2.602277 C 4.435702 0.473602 1.992293 C 3.129832 5.197598 3.222687 H 3.562454 1.985109 0.646625 H 2.451124 3.283189 3.029484 H 0.686483 3.123361 2.898662 H 0.045540 3.255281 0.475056 H 0.394235 4.551506 0.647057 H 0.146938 5.434116 1.679132 H 1.855068 6.515427 0.191648 H 2.383 853 6.544359 1.876463 H 4.243891 5.788631 0.375953 H 4.017414 3.673295 0.920643 H 2.786842 4.851021 1.408556 H 4.817012 3.682725 1.585926 H 4.115696 4.860704 2.699046 H 3.093619 2.595876 3.0 55490 H 0.699384 3.390593 2.931354 H 1.775605 4.677765 3.445990 H 0.725967 4.011241 3.665083 H 0.296946 1.186391 4.548202 H 0.697133 0.721419 2.888898 H 1.013731 2.371176 3.454052 H 0.868542 1.088422 4.098654 H 2.638974 1.096004 3.967655 H 4.730307 3.111397 2.446194 H 4.505083 0.339849 2.725714 H 5.411309 0.968472 1.960999 H 4.262200 0.006752 1.017355 H 2.889283 5.541714 4.236426 H 2.565134 5.820358 2.519471 H 4.198244 5.366098 3.053775 C 2.542995 3.594675 1.044819 H 2.715089 4.124673 1.980819 C 1.838822 4.427252 0.009731 H 2.493236 5.243784 0.327376 H 1.533233 3.842251 0.861111 N 0.197239 1.076436 3.237663 O 0.312314 1.325174 4.316471 O 0.685268 4.990241 0.669353 C 0.350965 1.017191 0.146089 H 0.022788 1.412622 0.789745 C 1.695766 0.319480 0.081563 H 1.807547 0.356946 0.935000 C 2.826358 1.383467 0.228761 H 2.610732 1.942446 1.150915 C 2.942874 2.321404 0.950183 H 3.426061 1.870590 1.815170

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287 O 1.785287 0.414839 1.135340 O 4.043145 0.65 9292 0.410638 C 2.629385 1.572801 1.087842 C 5.131427 1.447694 0.884165 C 2.506119 2.328347 2.389563 C 2.637268 1.665607 3.618534 C 2.296198 3.712547 2.392062 C 2.549582 2.369744 4.819593 H 2.805509 0.592852 3.628193 C 2.218765 4.422970 3.593656 H 2.195348 4.239371 1.446188 C 2.340621 3.752120 4.811342 H 2.652828 1.841277 5.763979 H 2.060537 5.498223 3.575837 H 2.278029 4.301121 5.747185 C 6.290040 0.543585 1.231698 C 7.590912 0.871063 0.835878 C 6.081329 0.618242 1.987195 C 8.669962 0.059881 1.195036 H 7.762007 1.765607 0.240795 C 7.155953 1.433808 2.339385 H 5.07 1693 0.883177 2.287068 C 8.454226 1.095319 1.947125 H 9.675243 0.327075 0.880020 H 6.980994 2.333732 2.923154 H 9.291205 1.730768 2.224218 H 2.329642 2.214825 0.247885 H 3.666855 1.263464 0. 915108 H 5.435605 2.188584 0.130362 H 4.803453 2.010858 1.775751 C 0.193206 5.812307 0.025321 O 1.076545 6.318253 0.678444 C 0.053558 6.017352 1.468317 H 0.565842 5.208180 2.006362 H 0.983071 6.057886 1.812444 H 0.559284 6.949505 1.724922 C 0.126039 1.535539 1.324008 C 2.806642 0.837752 0.905849 H 0.835070 2.354147 1.335469 H 0.373283 1.333879 2.268267 H 2.959625 1.557044 0.091164 C 3.584767 1.248938 2.134898 H 4.659387 1.286588 1.905332 H 3.424248 0.580990 2.979777 O 3.167505 2.606368 2.442429 C 2.601591 2.955809 3.629566 O 1.940974 3.971267 3.669041 C 2.8510 37 2.080753 4.839194 H 3.907447 1.808049 4.932311 H 2.265265 1.157151 4.769331 H 2.534807 2.634181 5.724180 TS15 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93460337000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.86399442000 a.u Ru 0.411603 1.135432 0.726275 O 0.887913 1.212590 3.209960 O 0.173306 0.387764 2.191948 N 0.291602 3.672106 0.481794 N 1.598563 3.149473 1.454399 C 0.698951 2.749456 0.500076 C 0.206764 4.655763 1.564136 C 1.489206 3.440670 0.329172 C 2.622997 2.812036 0.520021 C 3.831090 2.495350 0.382604 C 4.343472 3.797083 1.030396 C 3.215475 4.426156 1.874184 C 2.016832 4.754888 0.955433 C 2.787178 3.428924 2.972473 C 2.257694 2.123245 2.321626 C 1.034328 2.494856 1.457903 C 3.390698 1.503809 1.477300 C 2.961163 2.728976 1.623700 C 3.319370 2.028301 2.791214 C 4.661307 1.674802 2.971737 C 2.298368 1.673173 3.848496 C 1.233747 4.457545 2.046991 C 3.938962 3.123508 0.686412 C 5.648574 2.013453 2.042056 C 5.266458 2.748350 0.914273 C 3.582 875 3.930767 0.542610 C 7.083152 1.583863 2.237822 H 0.347467 3.076114 2.096611 H 0.397971 5.669709 1.202946 H 0.939673 4.426764 2.349228 H 2.259172 1.898088 1.003017 H 2.924318 3.508258 1.3 15902 H 4.627593 2.048242 0.227421 H 4.677290 4.501388 0.254872 H 5.214012 3.585820 1.665880 H 3.573820 5.355196 2.336686 H 1.212007 5.236034 1.527287 H 2.337398 5.463502 0.177184 H 2.009792 3.872616 3.608659 H 3.644912 3.206413 3.622957 H 1.970795 1.424831 3.114111 H 3.057237 0.564504 1.024029 H 4.242590 1.254300 2.124274 H 4.940419 1.119794 3.864775 H 2.065952 2.536223 4.486971 H 1.352018 1.338366 3.412673 H 2.675892 0.881792 4.502973 H 1.322679 4.427815 3.136083 H 1.908569 5.237429 1.671234 H 6.023578 3.040951 0.189882 H 3.055033 4.857302 0.287263 H 4.486519 4.2 06710 1.093781 H 2.929974 3.374399 1.225227

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288 H 7.325946 1.466178 3.298963 H 7.272346 0.619048 1.749643 H 7.781086 2.309084 1.806137 C 0.755347 4.125597 1.939274 H 1.113397 4.377385 2.936802 C 0.996935 5.195029 0.907474 H 0.156362 5.896476 0.892502 H 1.089114 4.782870 0.102326 N 0.237434 0.130107 3.308578 O 0.000111 0.424437 4.374545 O 2.132439 6.006187 1.247419 C 0.206183 0.075078 0.707785 H 0.104070 0.326094 1.769363 C 1.156160 1.121646 0.548781 H 1.755514 0.987316 0.359034 C 0.477362 2.518823 0.424793 H 0.310161 2.425517 0.337167 C 0.108508 2.970928 1.745990 H 0.057716 2.313528 2.595003 O 1.989352 1.012968 1.704793 O 1.383764 3.530187 0.031085 C 3.271623 1.659065 1.619886 C 1.568934 3.633006 1.454893 C 4.055347 1.309078 2.859206 C 3.752462 1.927594 4.080059 C 5.082998 0.360109 2.820611 C 4.460006 1.603181 5.237032 H 2.957365 2.668553 4.118055 C 5.798060 0.035562 3.975692 H 5.329354 0.121484 1.876837 C 5.486580 0.655965 5.186548 H 4.216 588 2.092771 6.176426 H 6.598085 0.698721 3.929000 H 6.043110 0.406981 6.086318 C 2.932669 3.173231 1.927223 C 4.095830 3.699119 1.345906 C 3.051938 2.261443 2.983256 C 5.354802 3.311360 1.8 02507 H 4.009115 4.413060 0.530642 C 4.314725 1.882426 3.449474 H 2.157949 1.844360 3.439670 C 5.467182 2.401806 2.858897 H 6.248525 3.724717 1.341990 H 4.393229 1.178757 4.274134 H 6.448379 2.105506 3.220692 H 3.796151 1.322436 0.715313 H 3.132343 2.741915 1.538412 H 1.441556 4.698685 1.688644 H 0.786346 3.075617 1.982486 C 3.414988 5.631039 0.951668 O 4.315022 6.325717 1.355329 C 3.622406 4.383549 0.117440 H 3.179850 3.503448 0.595137 H 3.160064 4.492164 0.870858 H 4.690636 4.216515 0.018260 C 1.912067 0.272986 0.440516 C 2.463281 0.331090 0.720843 H 2.166527 0.1 45304 1.405367 H 1.768456 1.347006 0.437560 H 3.124955 1.173323 0.550740 C 2.887310 0.533946 1.883996 H 3.076562 0.080505 2.765385 H 2.129414 1.284956 2.125283 O 4.098825 1.215867 1.470050 C 4.898246 1.859503 2.365279 O 5.831957 2.501816 1.944145 C 4.578323 1.721345 3.841680 H 4.686060 0.681730 4.172000 H 3.551968 2.029001 4.069388 H 5.277352 2.345876 4.398312 TS16 CB B3LYP/SDD/6 31G( d) SCF energy in gas p hase: 2839.95289771000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.87568890000 a.u Ru 0.574762 1.142129 0.938064 O 2.744518 0.090365 2.666643 O 0.602418 0.202460 2.242085 N 1.078706 3. 631783 0.402243 N 2.576055 2.264677 1.242721 C 1.572114 2.372394 0.321142 C 1.580246 4.387353 1.551840 C 0.110499 3.974443 0.377505 C 1.401190 3.783740 0.462008 C 2.641730 4.045984 0.413492 C 2.586645 5.485789 0.962501 C 1.304806 5.668028 1.801901 C 0.067542 5.426931 0.906148 C 1.313532 4.659575 2.969428 C 1.366571 3.207075 2.421521 C 0.104809 2.994392 1.568320 C 2.648967 3.03939 3 1.578878 C 3.675730 1.333879 1.223031 C 3.758754 0.313937 2.187651 C 4.858181 0.554342 2.148325 C 2.714649 0.119385 3.264437 C 2.785938 3.534491 1.978288 C 4.707665 1.520615 0.275376 C 5.883522 0.410533 1.210652 C 5.791400 0.640297 0.289942 C 4.648586 2.619454 0.762847 C 7.059870 1.357346 1.203457 H 0.790202 3.199951 2.192642 H 1.857164 5.408090 1.273111 H 0.816978 4.441286 2.339051 H 1.428652 2.764218 0.868084 H 1.390718 4.472895 1.318325 H 3.542019 3.913565 0.199074 H 2.606865 6.210569 0.136230

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289 H 3.470239 5.684896 1.583516 H 1.261802 6.691326 2.197121 H 0.858 705 5.584583 1.475224 H 0.068433 6.144158 0.072352 H 0.420805 4.793985 3.595685 H 2.185163 4.841613 3.612620 H 1.374991 2.514494 3.267939 H 2.720958 2.014126 1.201152 H 3.529593 3.200128 2.2 14593 H 4.898824 1.381732 2.851520 H 3.171937 0.189974 4.258988 H 1.915561 0.861585 3.204124 H 2.262648 0.876565 3.191641 H 2.820400 3.347816 3.055463 H 3.740010 3.986580 1.682581 H 6.583321 0.772797 0.444228 H 4.584348 3.617713 0.313203 H 5.544986 2.601141 1.389743 H 3.777264 2.511870 1.419517 H 7.708668 1.184657 2.072277 H 6.717893 2.395625 1.252147 H 7.670046 1.228037 0.303704 C 0.455448 3.441269 2.624437 H 0.711085 3.562664 3.676588 C 1.373156 4.182650 1.694393 H 1.320189 5.260104 1.901164 H 1.133257 4.025364 0.639810 N 1.585367 0.006361 3.087269 O 1.295719 0.2 43085 4.266495 O 2.711011 3.715197 1.977932 C 0.223312 0.225348 0.489516 H 0.580559 0.037593 1.484625 C 1.168041 0.857201 0.593206 H 1.699986 0.777207 0.357693 C 1.136008 2.372168 0.931580 H 0.537025 2.868583 0.156830 C 0.595190 2.675084 2.304828 H 1.161227 2.212217 3.110597 O 1.843761 0.096055 1.597311 O 2.485839 2.824993 0.806377 C 3.260783 0.011692 1.432744 C 2.643311 4.228057 0.634348 C 3.805015 1.042626 2.394292 C 3.222459 1.248647 3.651439 C 4.948649 1.776723 2.052941 C 3.771198 2.170185 4.545213 H 2.334081 0.686530 3.921289 C 5.503096 2.692936 2.948923 H 5.410078 1.627919 1.078880 C 4.914306 2.894050 4.198932 H 3.306696 2.319879 5.516880 H 6.391408 3.252620 2.667329 H 5.342293 3.609119 4.896641 C 4.008150 4.509388 0.049067 C 4.767789 5.589555 0.509950 C 4.508382 3.718669 0.994852 C 6.004321 5.887362 0.067341 H 4.391497 6.201348 1.327386 C 5.746878 4.010546 1.565665 H 3.931191 2.869141 1.348804 C 6.496827 5.097086 1.106628 H 6.58 4073 6.729749 0.301067 H 6.125963 3.388795 2.372430 H 7.460913 5.323297 1.554627 H 3.495334 0.294851 0.396943 H 3.728274 0.964514 1.611658 H 2.515597 4.760119 1.588946 H 1.858422 4.597311 0. 049070 C 3.803257 4.243778 1.351722 O 4.894958 3.888612 1.735625 C 3.588860 5.205290 0.204513 H 3.194994 4.686021 0.679901 H 2.890165 6.009128 0.457864 H 4.555731 5.638535 0.054044 C 1.334070 0.960596 0.355902 C 2.117073 0.054723 1.401864 H 2.086612 1.320141 0.349609 H 0.883375 1.780652 0.911547 H 3.093915 0.222342 1.015239 C 2.234991 0.651903 2.798804 H 2.980172 0.094298 3.37762 4 H 1.280809 0.638060 3.316952 O 2.720356 2.012834 2.642101 C 2.201092 3.051742 3.342493 O 2.435968 4.177522 2.955743 C 1.382426 2.754061 4.582595 H 1.905710 2.059272 5.248069 H 0.419026 2. 296740 4.330503 H 1.202303 3.696033 5.101467 TS17 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93137451000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.85439540000 a.u Ru 0.667605 0.975485 1.100834 O 2.271169 0.189346 2.194128 O 0.216141 0.099257 2.930136 N 0.864829 3.289462 0.599200 N 2.275482 1.871629 1.504689 C 1.417211 2.067037 0.456132 C 1.143833 3.905701 1.899667 C 0.109859 3.763297 0.390176 C 1.559696 3.485929 0.073858 C 2.553533 3.916500 1.023295 C 2.378151 5.420038 1.315470 C 0.934040 5.682303 1.790563 C 0.045643 5.276519 0.665031 C 0.657162 4.857547 3.067473 C 0.82358 0 3.344209 2.766622

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290 C 0.212740 2.972903 1.684017 C 2.273509 3.099095 2.298623 C 3.399577 0.970112 1.519062 C 3.408162 0.137229 2.388366 C 4.505485 1.007511 2.352421 C 2.302729 0.408595 3.385 183 C 2.332138 3.061291 2.386907 C 4.523671 1.259902 0.711753 C 5.606165 0.780143 1.522642 C 5.601346 0.370353 0.725945 C 4.604546 2.510663 0.138094 C 6.770620 1.741636 1.507325 H 1.190512 3.339220 2.032306 H 1.387922 4.966327 1.798623 H 0.273524 3.809434 2.561866 H 1.670138 2.416087 0.293429 H 1.766379 4.022903 1.010064 H 3.577004 3.724791 0.674677 H 2.595755 6.014413 0.416443 H 3.090787 5.736700 2.088815 H 0.803108 6.751146 2.005220 H 1.082480 5.491538 0.957362 H 0.171817 5.867581 0.237156 H 0.357711 5.062222 3.436339 H 1.353397 5.164492 3.860764 H 0.628230 2.765462 3.676866 H 2.440597 2.035054 2.110751 H 2.972046 3.397786 3.092934 H 4.486860 1.900565 2.971497 H 2.683373 0.297253 4.408807 H 1.456058 0.271484 3.266792 H 1.935048 1.436072 3.290599 H 2.244626 2.763985 3.435484 H 3.289561 3.580891 2.257194 H 6.460880 0.580596 0.092862 H 4.703559 3.412629 0.480018 H 5.482371 2.471740 0.790326 H 3.721440 2.651059 0.768990 H 7.341686 1.683 560 2.443314 H 6.416966 2.772330 1.405118 H 7.458916 1.521617 0.684873 C 0.093770 3.796958 2.435165 H 0.321482 4.056821 3.468276 C 1.005396 4.452536 1.437268 H 0.879446 5.543642 1.470826 H 0.825080 4.115231 0.413822 N 1.424170 0.356837 3.097841 O 1.671708 0.943628 4.153776 O 2.351106 4.122316 1.845011 C 0.358383 0.729235 0.393593 H 0.873166 0.466518 1.308449 C 1.131925 0.948856 0.602730 H 1.707959 0.694084 0.293505 C 1.423764 2.456045 0.865147 H 0.961224 3.009776 0.036063 C 0.915512 2.951169 2.196262 H 1.470837 2.562374 3.047741 O 1.501610 0.099965 1.687254 O 2.837 831 2.609746 0.775535 C 2.892989 0.216535 1.785502 C 3.289040 3.940361 0.535773 C 3.086715 1.281603 2.840481 C 2.260706 1.345820 3.970390 C 4.136647 2.200710 2.719722 C 2.478043 2.313354 4.9 53401 H 1.445016 0.636825 4.071220 C 4.360417 3.163292 3.705971 H 4.783347 2.164271 1.845498 C 3.529074 3.224597 4.826046 H 1.828774 2.351057 5.824850 H 5.179818 3.868740 3.594805 H 3.699097 3.975352 5.593298 C 4.698384 3.895560 0.005402 C 5.684170 4.746508 0.503728 C 5.021939 3.023311 1.054792 C 6.974843 4.739830 0.030976 H 5.442670 5.418416 1.324787 C 6.312043 3.011629 1.583594 H 4.265359 2.349283 1.447665 C 7.290966 3.871321 1.076037 H 7.731556 5.406774 0.374025 H 6.552465 2.331665 2.396560 H 8.294988 3.861201 1.492273 H 3.266987 0.568688 0.813604 H 3.463417 0.6 86107 2.037060 H 3.243942 4.541914 1.455815 H 2.617248 4.418610 0.197741 C 3.444027 4.558227 1.155638 O 4.534515 4.313382 1.620729 C 3.238157 5.283467 0.156205 H 2.956800 4.580607 0.952084 H 2.462393 6.052975 0.097587 H 4.185642 5.745976 0.435267 C 1.096613 1.345476 0.610901 C 2.304931 0.426702 1.768833 H 2.140421 1.587988 0.450902 H 0.611370 1.869354 1.428296 H 3.194370 0.374811 1.134659 C 2.594203 0.065519 3.171207 H 3.425022 0.526023 3.581717 H 1.732661 0.005925 3.827991 O 3.060811 1.431830 3.045605 C 2.428314 2.470581 3.663658 O 2.581072 3.581173 3.202256 C 1.609479 2.188722 4.904236 H 2.130121 1.506915 5.584713 H 0.641008 1.738942 4.650857 H 1.428964 3.140287 5.406147

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291 TS18 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93485600000 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 2838.85788138000 a.u Ru 0.598635 0.957130 1.097477 O 0.231463 2.343730 1.726960 O 0.646678 0.289311 2.419032 N 0.857126 3.734397 0.328281 N 2.520290 2.756544 0.710922 C 1.48276 8 2.544303 0.152382 C 1.340223 4.791961 0.565026 C 0.413339 3.793381 1.055263 C 1.612331 3.782081 0.070491 C 2.936468 3.743093 0.857307 C 3.030108 4.986561 1.763988 C 1.838661 4.997718 2.745 192 C 0.516288 5.055798 1.945085 C 1.879040 3.716923 3.605208 C 1.777371 2.463457 2.697374 C 0.445191 2.532229 1.933634 C 2.967194 2.464319 1.716767 C 3.658576 1.912121 0.956921 C 3.734105 1.164295 2.148080 C 4.865390 0.370429 2.367741 C 2.631201 1.160325 3.183467 C 2.644415 4.181339 1.094368 C 4.730040 1.915056 0.037690 C 5.926525 0.322726 1.459539 C 5.842537 1.112988 0.308499 C 4.709711 2.761498 1.217436 C 7.117034 0.568373 1.719119 H 0.377648 2.628700 2.693723 H 1.496945 5.731542 0.027843 H 0.615218 4.973734 1.368797 H 1.536666 2.908678 0.586264 H 1.581928 4.680 063 0.562986 H 3.772410 3.735530 0.146225 H 3.029832 5.901788 1.154938 H 3.974849 4.976207 2.324109 H 1.899816 5.882538 3.392440 H 0.345339 5.097023 2.625540 H 0.495822 5.970216 1.334109 H 1.056020 3.722385 4.333699 H 2.813675 3.687483 4.182696 H 1.803260 1.557883 3.307898 H 2.919481 1.578239 1.074443 H 3.910719 2.408043 2.277193 H 4.899810 0.258750 3.252768 H 3.031191 1.413478 4.172396 H 1.835289 1.869508 2.945018 H 2.183064 0.162456 3.269246 H 2.758149 4.275499 2.178169 H 3.529961 4.621767 0.620746 H 6.662929 1.098852 0.406077 H 4.904268 3.819769 0.997824 H 5.487362 2.432404 1.913409 H 3.747742 2.715589 1.738672 H 7.652494 0.259995 2.626120 H 6.789125 1.602308 1.869444 H 7.827086 0.541921 0.886220 C 0.301408 2.699676 3.100272 H 0.471643 2.681435 4.176408 C 1.309285 3.516021 2.342916 H 1.322317 4.539865 2.738202 H 1.098666 3.569836 1.271885 N 0.818756 1.575686 2.521821 O 1.552895 1.989585 3.423861 O 2.599458 2.902210 2.569556 C 0.11 8210 0.350328 0.510035 H 0.293883 0.657638 1.478613 C 1.396460 0.451895 0.694450 H 1.950120 0.520296 0.246877 C 1.173353 1.914219 1.167678 H 0.439846 2.357394 0.491992 C 0.742059 2.018926 2. 607725 H 1.386150 1.493867 3.309860 O 2.136558 0.333561 1.636942 O 2.428351 2.572752 0.960422 C 3.560535 0.176754 1.584779 C 2.337058 3.989483 0.771741 C 4.207341 1.214279 2.471699 C 3.649686 1.556694 3.710987 C 5.408419 1.819510 2.082045 C 4.281227 2.483900 4.540428 H 2.713869 1.098991 4.016712 C 6.046417 2.741514 2.914833 H 5.849312 1.565113 1.120652 C 5.483284 3.077509 4.14680 9 H 3.835605 2.741757 5.497961 H 6.978750 3.200970 2.596939 H 5.975481 3.797886 4.794889 C 3.577509 4.459877 0.054468 C 4.602441 5.118503 0.741078 C 3.719816 4.216947 1.319825 C 5.755047 5. 534498 0.070412 H 4.497364 5.306757 1.807488 C 4.871241 4.629292 1.989630 H 2.927146 3.708721 1.864544 C 5.890749 5.289170 1.296712 H 6.543589 6.048125 0.614488 H 4.970588 4.438873 3.054981 H 6.785734 5.612848 1.822081 H 3.912331 0.288943 0.549598 H 3.827147 0.838337 1.904834 H 2.228047 4.497297 1.741465 H 1.447926 4.212413 0.165064 C 3.757149 3.475541 2.126678 O 4.799434 2.94493 7 2.440117 C 3.672448 4.710090 1.257472

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292 H 3.278779 4.472483 0.260054 H 3.030557 5.482890 1.692346 H 4.681713 5.106572 1.141004 C 1.987809 0.807574 0.152277 C 2.472789 0.345695 1.368662 H 2.385317 0.431258 0.778534 H 1.468545 1.754391 0.127480 H 3.270298 0.388618 1.332010 C 2.489958 1.253523 2.591761 H 3.238737 0.886304 3.304191 H 1.528027 1.297057 3.094980 O 2.884776 2.565992 2.140910 C 2.467932 3.717345 2.731819 O 2.700042 4.757910 2.156143 C 1.759208 3.644182 4.066655 H 2.222599 2.924381 4.748910 H 0.712197 3.356823 3.917450 H 1.781930 4.639200 4.513216 TS19 CB B 3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.92739493000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.85871193000 a.u Ru 0.461156 0.927429 0.783822 O 0.949284 0.614439 3.367998 O 0.378840 0.580137 2.118927 N 0.050488 3.606508 0.244242 N 1.793667 2.939774 1.383804 C 0.927835 2.580836 0.382375 C 0.168258 4.634234 1.282860 C 1.133668 3.459797 0.606933 C 2.361128 3.005827 0.225307 C 3.563755 2.769055 0.708809 C 3.907785 4.082039 1.440500 C 2.688810 4.541933 2.266534 C 1.492288 4.787087 1.319469 C 2.332157 3.447962 3.295069 C 1.975465 2.129649 2.559711 C 0.753734 2.402853 1.660606 C 3.19 4725 1.677798 1.732594 C 3.065899 2.377992 1.746116 C 3.170087 1.618965 2.928542 C 4.431967 1.147782 3.310078 C 1.965567 1.295424 3.783069 C 1.543831 4.317545 1.869093 C 4.217210 2.720165 1. 005002 C 5.583194 1.422135 2.567208 C 5.453589 2.220943 1.426141 C 4.153256 3.621668 0.209175 C 6.926405 0.865044 2.974521 H 0.038006 2.847730 2.292330 H 0.106325 5.640791 0.861764 H 0.632913 4.521644 2.025521 H 2.114137 2.088086 0.771232 H 2.612437 3.774891 0.969608 H 4.425848 2.443720 0.110553 H 4.190661 4.858306 0.715094 H 4.772318 3.931244 2.100652 H 2.926634 5.478729 2.787313 H 0.621032 5.147355 1.882785 H 1.758117 5.566748 0.590350 H 1.487006 3.770042 3.918242 H 3.183312 3.284235 3.970958 H 1.739334 1.365850 3.305666 H 2.973123 0.734950 1.221102 H 4.0467 29 1.481568 2.396989 H 4.515196 0.553044 4.217112 H 2.273006 1.062536 4.807022 H 1.248288 2.120306 3.819712 H 1.421967 0.422118 3.401723 H 1.570910 4.350011 2.961739 H 2.319429 4.993695 1.48 8837 H 6.340952 2.466093 0.846373 H 4.122105 4.680414 0.080955 H 5.041823 3.488135 0.833481 H 3.271922 3.427607 0.826986 H 6.955039 0.627868 4.042827 H 7.147971 0.059832 2.426453 H 7.735687 1.571062 2.759267 C 0.534146 4.262695 1.795805 H 0.943542 4.596138 2.748548 C 0.703557 5.248371 0.671272 H 0.131718 5.957358 0.672547 H 0.710636 4.762675 0.309476 N 0.123521 0.337918 3.292449 O 0.210160 1.024805 4.252559 O 1.868236 6.065202 0.864209 C 0.209302 0.014013 0.723466 H 0.046122 0.339190 1.755220 C 1.278587 1.086456 0.681505 H 1.958222 0.883762 0.155657 C 0.763530 2.54 4763 0.474681 H 0.039384 2.516972 0.351449 C 0.115912 3.094965 1.729350 H 0.238195 2.504221 2.633527 O 1.971208 0.910609 1.918204 O 1.816408 3.437997 0.092823 C 3.300531 1.454141 1.982013 C 2.088692 3.553269 1.315235 C 3.963091 0.922489 3.227571 C 3.843508 1.606928 4.443368 C 4.685611 0.276972 3.197216 C 4.431452 1.104776 5.605277 H 3.287257 2.540986 4.476754 C 5.277030 0.782660 4.355614 H 4.790355 0.812617 2.256034 C 5.150093 0.091971 5.563130 H 4.333299 1.648915 6.541001 H 5.840950 1.711031 4.315442

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293 H 5.613603 0.481752 6.465636 C 3.406852 2.937210 1.737026 C 4.585484 3.230796 1.035705 C 3.475543 2.120263 2.872084 C 5.808825 2.708707 1.454727 H 4.538221 3.870204 0.158026 C 4.704394 1.608065 3.299632 H 2.566457 1.880838 3.417949 C 5.871550 1.896775 2.591541 H 6.714956 2.941799 0.901167 H 4.744866 0.979799 4.185764 H 6.826067 1.496229 2.923212 H 3.859392 1.158858 1.083313 H 3.254903 2.548616 1.998787 H 2.110605 4.632420 1.520088 H 1.272 491 3.115065 1.899956 C 3.111610 5.695250 0.426336 O 4.047030 6.393688 0.730051 C 3.233157 4.453167 0.433455 H 2.845808 3.568301 0.082543 H 2.672766 4.566580 1.369244 H 4.282954 4.290199 0.6 77484 C 1.832187 0.581908 0.409996 C 2.183826 0.381324 0.954266 H 1.485161 1.560548 0.720587 H 2.376535 0.039555 1.173052 H 1.885120 1.179995 1.633063 C 3.486212 0.260742 1.366800 H 3.386388 0.781852 2.320576 H 3.847941 0.951428 0.609831 O 4.499730 0.769745 1.445862 C 4.737897 1.471877 2.591514 O 5.396871 2.482577 2.512736 C 4.213717 0.920957 3.904738 H 3.127436 0.786385 3.910540 H 4.660541 0.057757 4.117436 H 4.496899 1.618644 4.693128 TS20 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.92130330000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.85652192000 a.u Ru 1.723287 0.234328 0.5 28300 O 1.943014 2.068787 3.343040 O 0.440368 1.295704 1.916752 N 3.676185 0.343145 1.606830 N 3.140046 1.786719 1.518546 C 2.886083 0.554012 0.964631 C 4.383980 0.208894 2.765469 C 3.379899 1.774778 1.438245 C 2.259935 2.203853 2.424972 C 1.873561 3.674890 2.178267 C 3.116011 4.564877 2.383964 C 4.224140 4.138997 1.398206 C 4.616832 2.667403 1.671990 C 3.698240 4.288761 0.045332 C 2.455924 3.383428 0.256285 C 2.891950 1.924094 0.015420 C 1.356417 3.814494 0.732672 C 2.297166 2.954217 1.505801 C 1.163278 2.969791 2.354473 C 0.368589 4.117592 2.391200 C 0.808458 1.787371 3.228990 C 4.203581 1.718509 2.550820 C 2.666127 4.106477 0.787879 C 0.673761 5.256652 1.634433 C 1.831918 5.232608 0.858110 C 3.933465 4.202509 0.031966 C 0.219815 6.473935 1.672782 H 3.763667 1.742041 0.662262 H 5.435223 0.091287 2.768293 H 3.927538 0.138842 3.702146 H 1.382751 1.558409 2.281111 H 2.595738 2.070904 3.463726 H 1.084636 3.963033 2.884234 H 3.475023 4.483 120 3.420092 H 2.855768 5.619136 2.219698 H 5.108728 4.773641 1.539901 H 5.429107 2.354752 1.001668 H 4.986566 2.571799 2.704134 H 4.482152 4.022451 0.767323 H 3.435341 5.339179 0.234205 H 2.108279 3.496270 1.286003 H 0.459441 3.199155 0.597808 H 1.062469 4.855481 0.539068 H 0.502245 4.129877 3.043593 H 1.648324 1.484112 3.865306 H 0.515529 0.908275 2.644147 H 0.028479 2.038370 3.887033 H 3.893771 2.249068 3.455146 H 5.119838 2.193171 2.178038 H 2.114108 6.121305 0.297364 H 4.368584 5.202861 0.065131 H 3.746985 4.038780 1.099882 H 4.687794 3.479243 0.287708 H 0.589 690 6.667900 2.685680 H 1.098582 6.339033 1.028774 H 0.306365 7.368479 1.325328 C 3.930177 1.838320 1.595716 H 3.918952 2.416002 2.520357 C 5.136171 0.944588 1.480804 H 5.000946 0.059132 2.1 12199 H 5.311470 0.609314 0.460660 N 0.759980 2.021203 2.965900 O 0.162186 2.614323 3.530123 O 6.295706 1.593318 2.046685 C 0.026815 1.208575 0.369645 H 0.109742 1.704946 0.583869 C 1.310719 0.418181 0.483087

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294 H 1.290286 0.173312 1.401307 C 2.573817 1.344501 0.557620 H 2.323254 2.155828 1.263512 C 2.888597 1.985620 0.767838 H 2.100215 2.665894 1.090938 O 1.328804 0.453914 0.649086 O 3.684596 0.615287 1.074370 C 2.136329 1.630892 0.499604 C 3.716032 0.539424 2.511191 C 2.245360 2.336066 1.830635 C 2.377284 1.610165 3.022918 C 2.272690 3.734991 1.885358 C 2.531567 2.2 71780 4.242196 H 2.351981 0.525530 2.985361 C 2.434258 4.397975 3.103998 H 2.165109 4.309332 0.968078 C 2.562161 3.667849 4.287095 H 2.632665 1.696203 5.158980 H 2.454432 5.484426 3.128128 H 2.684937 4.182180 5.236569 C 4.545932 0.643833 2.937248 C 5.941083 0.545546 3.012953 C 3.928456 1.863821 3.245795 C 6.712065 1.649391 3.378544 H 6.424063 0.404415 2.793626 C 4.699186 2.967738 3.615352 H 2.843913 1.951800 3.210282 C 6.090463 2.863761 3.679015 H 7.793750 1.560815 3.435437 H 4.209589 3.906482 3.859490 H 6.688587 3.723554 3.969242 H 1.686322 2.288214 0.256581 H 3.1 30649 1.344812 0.139042 H 4.131689 1.480500 2.902283 H 2.698241 0.433036 2.906184 C 7.053434 2.462294 1.323161 O 7.945122 3.054889 1.882689 C 6.757900 2.612248 0.158293 H 5.708035 2.858553 0.343207 H 6.973185 1.677434 0.689071 H 7.401049 3.400609 0.550405 C 0.643506 1.751250 1.467098 C 2.613929 0.540692 1.952167 H 0.305627 1.531103 2.476171 H 1.250455 2.642263 1.349138 H 2.2361 35 0.246189 2.936456 C 3.893745 1.310930 2.014807 H 4.694585 0.587531 2.231648 H 4.133459 1.796127 1.072244 O 3.865947 2.364502 2.994982 C 4.141075 2.159139 4.322988 O 3.987302 3.086643 5.07 7575 C 4.649632 0.796718 4.754083 H 3.950274 0.009424 4.507935 H 5.608359 0.564081 4.275385 H 4.794771 0.826726 5.834131 TS21 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93279127000 a.u. M06/SDD/6 311++G(d, p) SCF energy in solution : 2838.8505284200 a.u Ru 1.449748 0.302537 0.758244 O 0.718541 2.383530 0.105729 O 0.181494 1.571018 2.043272 N 4.086736 0.126178 0.443924 N 2.880350 1.309134 1.584541 C 2.838703 0.408209 0.553067 C 5.012272 0.292404 1.500847 C 4.288143 1.348072 0.344012 C 4.127920 2.606261 0.551289 C 4.282608 3.884334 0.298980 C 5.666700 3.893405 0.976082 C 5.799349 2.650575 1.879199 C 5.687740 1.382703 1.002176 C 4.678465 2.669975 2.944159 C 3.287248 2.638729 2.250651 C 3.219331 1.316379 1.448793 C 3.178063 3.905184 1.372468 C 1.792127 1.908499 2.308716 C 1.08 6280 1.117791 3.243082 C 0.065621 1.719109 3.984981 C 1.412736 0.343813 3.456392 C 4.220936 1.403771 2.204119 C 1.531237 3.286746 2.188371 C 0.257452 3.072436 3.838965 C 0.492197 3.839743 2. 945715 C 2.326556 4.203804 1.284912 C 1.376587 3.704149 4.632670 H 3.546012 0.537738 2.150354 H 5.955423 0.652081 1.078417 H 5.241420 0.543525 2.173831 H 3.141301 2.587124 1.027924 H 4.884696 2.599995 1.348688 H 4.183962 4.762569 0.352640 H 6.465047 3.897704 0.219852 H 5.786881 4.807721 1.572778 H 6.779177 2.655744 2.375164 H 5.828255 0.477022 1.608116 H 6.483930 1.394353 0.24262 8 H 4.784566 1.810509 3.620837 H 4.773529 3.575283 3.560350 H 2.502446 2.649242 3.016036 H 2.200981 3.979723 0.892646 H 3.293117 4.795405 2.006836 H 0.492958 1.109814 4.692083 H 0.844269 0. 741807 4.301631 H 2.478251 0.496565 3.668840 H 1.168660 0.956349 2.581121 H 4.145812 1.257886 3.286051

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295 H 4.648438 2.398503 2.030122 H 0.246883 4.887787 2.798039 H 2.754114 5.030691 1.864213 H 1.685680 4.660735 0.522071 H 3.149749 3.685232 0.788274 H 1.988135 2.949401 5.137632 H 2.026720 4.295138 3.977861 H 0.987155 4.384620 5.401076 C 3.451785 2.595057 1.258546 H 3.732351 2.981419 2.237376 C 3.147490 3.669438 0.255414 H 4.035134 4.297676 0.099906 H 2.837994 3.269964 0.714198 N 0.119617 2.565308 1.223566 O 0.470093 3.599601 1.495000 O 2.091364 4.477086 0.823531 C 0.549164 0.349636 0.301861 H 0.245760 0.339854 1.341554 C 1.827948 0.444278 0.063761 H 1.756188 1.063732 0.837805 C 3.057561 0.500168 0.152417 H 2.821805 1.178716 0.984053 C 3.412064 1.269 267 1.091604 H 3.666840 0.634972 1.936795 O 1.999707 1.261496 1.211255 O 4.220468 0.258896 0.495781 C 2.735707 2.484179 1.027402 C 4.325996 0.610372 1.870839 C 2.481788 3.373894 2.218602 C 3.410633 3.454925 3.261894 C 1.298291 4.120839 2.302201 C 3.166448 4.265536 4.372817 H 4.332902 2.880990 3.201555 C 1.051780 4.930980 3.410592 H 0.579183 4.064830 1.489544 C 1.984801 5.004676 4.449004 H 3.898426 4.321959 5.174610 H 0.133897 5.511413 3.461914 H 1.793619 5.639856 5.310376 C 5.658443 1.279944 2.117669 C 6.812064 0.845393 1.452710 C 5.760656 2.320552 3.047431 C 8.045197 1.441286 1.717224 H 6.730651 0.051046 0.717474 C 6.996158 2.911439 3.319632 H 4.867938 2.675348 3.558015 C 8.142142 2.473292 2.654232 H 8.932752 1.100058 1.190414 H 7.059697 3.720422 4.042589 H 9.103641 2.936633 2.859215 H 2.392138 2.975600 0.107176 H 3.804045 2.267138 0.923063 H 4.239121 0.305138 2.483563 H 3.509385 1.279589 2.178924 C 1.553555 5.542977 0.169057 O 0.671 893 6.161374 0.724993 C 2.046409 5.879998 1.221607 H 1.520249 5.263144 1.962666 H 3.122278 5.734744 1.350410 H 1.792204 6.921991 1.422020 C 0.178977 1.472705 0.446110 C 1.427961 1.167397 1.9 20744 H 0.766256 1.764084 1.312860 H 0.343801 2.280599 0.048301 H 0.829528 0.977163 2.829545 C 2.095615 2.507595 1.984574 H 2.926732 2.445805 2.701734 H 2.503138 2.811321 1.023148 O 1.172004 3.562446 2.349736 C 0.851164 3.860488 3.635499 O 0.119130 4.556343 3.837233 C 1.744897 3.345770 4.747451 H 1.751232 2.251344 4.790376 H 2.779239 3.680976 4.609865 H 1.363631 3.735749 5.691290 TS22 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.92569543000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.85412322000 a.u Ru 0.905414 0.800846 0.953725 O 0.889493 1.658888 2.577245 O 0.643008 0.538080 2.4 92488 N 2.615576 2.903357 0.044554 N 3.216039 1.169293 1.250905 C 2.358251 1.586240 0.267931 C 3.695282 3.456686 0.867295 C 1.629539 3.726242 0.661155 C 0.676896 4.394730 0.368117 C 0.432215 5.172783 0.363258 C 0.211138 6.256486 1.252127 C 1.149818 5.590380 2.280117 C 2.272656 4.827894 1.535802 C 0.330486 4.613218 3.150033 C 0.305352 3.514306 2.258180 C 0.828007 2.766664 1.543715 C 1.238620 4.186427 1.229981 C 3.126572 0.017699 2.064289 C 2.160032 0.077276 3.092103 C 2.084993 1.238819 3.868766 C 1.251790 1.085565 3.437024 C 4.028932 2.280306 1.798351 C 4.077188 1.0 50027 1.913663 C 2.958451 2.314208 3.688314 C 3.959132 2.186627 2.719712 C 5.230193 0.978130 0.935961 C 2.845528 3.574020 4.510572 H 1.532705 2.372206 2.336570 H 4.546797 3.748349 0.241532

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296 H 3.360680 4.343388 1.415252 H 0.239802 3.611963 1.000356 H 1.244971 5.073271 1.020423 H 1.089959 5.645041 0.378379 H 0.770225 6.972098 0.632412 H 0.568122 6.828178 1.773465 H 1.607054 6.360184 2.915202 H 2.967588 4.369473 2.252637 H 2.853363 5.529856 0.919585 H 0.971947 4.152415 3.913917 H 0.455371 5.163079 3.686293 H 0.870926 2.812148 2.874245 H 1.708170 3.422559 0.597138 H 2.047315 4.715218 1.752144 H 1.322206 1.298488 4.642257 H 1.101189 1.772931 2.602788 H 0.264273 0.735081 3.752084 H 1.672104 1.660976 4.273750 H 3.740473 2.470045 2.838868 H 5.090902 2.017040 1.787021 H 4.668219 2.999941 2.581936 H 6.166473 1.240026 1.441888 H 5.107146 1.685761 0.107956 H 5.349640 0.020459 0.508276 H 2.021537 3.510703 5.228491 H 2.673954 4.434313 3.854505 H 3.76 8919 3.764407 5.072054 C 1.401772 3.492116 2.019125 H 1.445258 3.836214 3.051784 C 0.662352 4.423687 1.104603 H 1.167389 5.398766 1.071476 H 0.594407 4.041584 0.082579 N 1.210390 0.526173 2. 999641 O 2.050917 0.352727 3.882206 O 0.657780 4.597401 1.668977 C 0.100612 0.018602 0.424645 H 0.302949 0.197815 1.415292 C 1.606379 0.186937 0.369415 H 2.017940 0.272784 0.532992 C 2.074189 1.667254 0.354864 H 1.483952 2.191068 0.402015 C 1.985105 2.328393 1.706554 H 2.490549 1.780957 2.498417 O 2.079076 0.512003 1.529405 O 3.436126 1.624738 0.090260 C 3.357579 1.145590 1.358364 C 3.900572 2.840677 0.685144 C 3.703826 1.882240 2.628118 C 4.851186 1.548766 3.355423 C 2.884887 2.919491 3.096436 C 5.181765 2.239846 4.524006 H 5.491559 0.743785 3.002381 C 3.20717 9 3.606637 4.265549 H 1.990149 3.184073 2.538425 C 4.359312 3.269150 4.982401 H 6.078752 1.970943 5.075703 H 2.564141 4.409666 4.617038 H 4.613317 3.807513 5.891759 C 5.170213 2.553519 1.446 028 C 6.415889 2.946372 0.945897 C 5.107592 1.869879 2.669256 C 7.586876 2.668010 1.654809 H 6.469462 3.474515 0.003873 C 6.276458 1.588743 3.375909 H 4.143242 1.561328 3.067234 C 7.517896 1.987900 2.871575 H 8.548928 2.981739 1.257675 H 6.217328 1.061011 4.324124 H 8.427051 1.771181 3.426781 H 3.297223 1.843309 0.507950 H 4.119220 0.395885 1.120254 H 4.073386 3.604283 0.088103 H 3.127862 3.216002 1.372384 C 1.579409 5.422798 1.103249 O 2.627672 5.593802 1.683169 C 1.246802 6.065906 0.227610 H 1.069251 5.307367 0.998382 H 0.345245 6.684944 0.160775 H 2.090717 6.687 386 0.526867 C 1.436346 1.493473 0.568057 C 1.918943 0.947210 1.773455 H 0.581512 2.152905 0.626020 H 2.076843 1.592986 0.299882 H 1.344579 1.210653 2.659129 C 3.385316 0.668657 2.012640 H 3.524391 0.010161 2.859410 H 3.848434 0.222318 1.136414 O 4.122997 1.894684 2.228834 C 4.266490 2.473040 3.456490 O 4.830305 3.537886 3.522857 C 3.739498 1.733970 4.673662 H 2.671359 1.509270 4.591447 H 4.270738 0.786460 4.821517 H 3.905790 2.369307 5.543806 17 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.94180388000 a .u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.87647071000 a.u Ru 0.008080 1.287532 0.748837 O 0.325624 0.918862 3.846877 O 0.359693 0.320223 2.156161 N 1.050354 3.714571 0.424453 N 0.619497 3.246108 1.757230 C 0.029162 2.836238 0.629466 C 1.237546 4.674435 1.518520 C 2.121117 3.358555 0.511323 C 3.235661 2.554905 0.215653 C 4.305216 2.097651 0.794950

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297 C 4.923327 3.337886 1.471909 C 3.819200 4.133389 2.199288 C 2.758363 4.600269 1.176299 C 3.155608 3.23 0459 3.258720 C 2.531487 1.983421 2.578114 C 1.468223 2.470447 1.583115 C 3.642166 1.196727 1.855089 C 1.739006 2.649622 2.429191 C 1.515980 1.649077 3.396997 C 2.629437 1.075781 4.025263 C 0.131237 1.227141 3.840993 C 0.057956 4.494090 2.319020 C 3.036884 3.159527 2.205696 C 3.934512 1.493268 3.755397 C 4.112710 2.555550 2.861017 C 3.288008 4.376296 1.340240 C 5.121492 0.827056 4.409924 H 0.697751 3.060316 2.124689 H 1.360823 5.692305 1.138840 H 2.127137 4.420126 2.109425 H 2.785435 1.686663 0.715932 H 3.698653 3.176803 0.994554 H 5.085525 1.538006 0.263038 H 5.41 9205 3.972165 0.723632 H 5.694537 3.028720 2.189695 H 4.256774 5.015881 2.683472 H 1.977744 5.193078 1.671479 H 3.229731 5.244213 0.419431 H 2.382190 3.785907 3.805952 H 3.902286 2.911443 3. 998840 H 2.066789 1.364661 3.346496 H 3.227029 0.295230 1.388516 H 4.393065 0.859518 2.582055 H 2.464327 0.287584 4.757092 H 0.050239 1.570263 4.868152 H 0.655347 1.640813 3.207285 H 0.013910 0.138639 3.841985 H 0.109437 4.383601 3.394287 H 0.757883 5.324116 2.165911 H 5.117054 2.928059 2.670791 H 3.268437 5.290286 1.949390 H 4.276306 4.327362 0.872299 H 2.541632 4.493399 0.55005 6 H 4.827575 0.277636 5.309806 H 5.595109 0.110963 3.726053 H 5.886931 1.558722 4.690954 C 2.405126 4.071059 0.682960 H 3.078484 4.366748 1.486682 C 2.641688 4.785965 0.619756 H 2.082032 5.727248 0.635444 H 2.306670 4.199194 1.481420 N 0.099857 0.176520 3.434756 O 0.299468 1.151191 4.164564 O 4.013316 5.188627 0.764285 C 0.276865 0.202627 0.568380 H 0.209260 0.098352 1.608438 C 0.456001 1.558256 0.434871 H 1.301967 1.457159 0.256262 C 0.404208 2.739439 0.092457 H 0.903195 2.388851 1.007007 C 1.428555 3.190765 0.928092 H 1.317219 2.790006 1.932149 O 0.958575 1.791 299 1.756398 O 0.387741 3.880563 0.449634 C 2.071961 2.685872 1.866174 C 0.952667 3.883315 1.774064 C 2.645686 2.560843 3.256965 C 1.855412 2.856957 4.377235 C 3.970883 2.159150 3.455991 C 2.378589 2.750502 5.665237 H 0.825529 3.172906 4.232009 C 4.501531 2.058895 4.744971 H 4.594179 1.929497 2.594544 C 3.705720 2.352394 5.852615 H 1.754906 2.985440 6.524098 H 5.534765 1.750186 4.881803 H 4.115868 2.275229 6.856192 C 2.460924 3.739206 1.778650 C 3.257552 4.594265 1.003093 C 3.082548 2.781904 2.589626 C 4.647625 4.486209 1.026602 H 2.780333 5.342736 0.375510 C 4.477 007 2.681074 2.622558 H 2.468335 2.124164 3.198828 C 5.262052 3.527889 1.839050 H 5.253209 5.154251 0.419187 H 4.947843 1.939109 3.262692 H 6.345940 3.448467 1.864412 H 2.830468 2.435136 1.1 12272 H 1.745506 3.713596 1.668265 H 0.679688 4.855016 2.208016 H 0.502145 3.099489 2.391843 C 4.986226 4.329739 1.197071 O 6.125647 4.726811 1.211535 C 4.571915 2.944669 1.652242 H 4.020989 2.416125 0.867178 H 3.923421 3.001255 2.535057 H 5.463020 2.372183 1.909255 C 1.768448 0.005482 0.050338 C 1.907696 0.949603 1.198607 H 2.145869 0.967538 0.263743 H 2.372461 0.393420 0.870245 H 1.943798 0.373061 2.122912 C 3.029254 1.957021 1.186261 H 2.862371 2.733918 1.938831 H 3.138693 2.423789 0.211930 O 4.292672 1.290080 1.412952 C 4.744466 0.992871 2.667316

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298 O 5.688645 0.2 45471 2.768844 C 4.070411 1.648690 3.858739 H 3.011290 1.381069 3.942708 H 4.132945 2.741387 3.793784 H 4.593525 1.317181 4.756019 17 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.94755020000 a.u. M06/SDD /6 311++G(d,p) SCF energy in solution: 2838.87315335000 a.u Ru 0.030380 1.300170 0.932276 O 2.878416 0.277763 1.263998 O 1.071469 0.287898 2.510296 N 0.696769 3.807087 0.350340 N 2.105221 2.398978 1.273744 C 1.067884 2.498796 0.389228 C 1.441810 4.678268 1.264074 C 0.610868 4.163745 0.202682 C 1.681107 4.172168 0.923640 C 3.072969 4.461519 0.331603 C 3.054115 5.828844 0.380122 C 2.000572 5.807983 1.507018 C 0.603960 5.544979 0.899775 C 2.352875 4.691241 2.512057 C 2.362511 3.313078 1.793793 C 0.953331 3.080867 1.231347 C 3.418578 3.345046 0.670659 C 2.591663 1.230468 1.967442 C 1.789672 0.672100 2.988836 C 2.297059 0.411093 3.712534 C 0.407501 1.196051 3.309167 C 2.442541 3.700601 1.900023 C 3.901937 0.763293 1.743758 C 3.567820 0.939221 3.466762 C 4.355654 0.33 1972 2.487007 C 4.858835 1.394270 0.755000 C 4.097597 2.120249 4.243913 H 0.222280 3.156945 2.076713 H 1.936702 5.485760 0.714306 H 0.775239 5.134678 2.004674 H 1.677429 3.196343 1.424889 H 1.425996 4.932179 1.675094 H 3.811217 4.475587 1.143793 H 2.826156 6.630095 0.337154 H 4.044833 6.048398 0.799680 H 1.987603 6.778081 2.020540 H 0.167534 5.557927 1.681770 H 0.354423 6.339005 0.180942 H 1.631252 4.681900 3.340745 H 3.341204 4.882367 2.951843 H 2.611749 2.534167 2.517313 H 3.453523 2.374633 0.167546 H 4.411134 3.521007 1.106962 H 1.676963 0.853363 4.489251 H 0.091136 0.850657 4.297835 H 0.365800 2.291020 3.310258 H 0.338828 0.837737 2.590900 H 2.334078 3.625764 2.986839 H 3.483291 3.964678 1.685901 H 5.341990 0.735781 2.274035 H 5.844968 1.520204 1.215230 H 5.001411 0.759187 0.127056 H 4.522400 2.376344 0.413160 H 3.311480 2.593433 4.841662 H 4.516331 2.866927 3.561276 H 4.899958 1.818402 4.929610 C 1.821508 3.841915 1.395134 H 2.18 4308 4.141849 2.376960 C 2.868201 3.942440 0.321898 H 3.109721 4.996867 0.126560 H 2.557704 3.482187 0.620181 N 2.324564 0.043607 2.334336 O 2.884899 0.674941 3.232339 O 4.042445 3.281230 0. 841346 C 0.340167 0.462782 0.044782 H 0.811920 0.368393 1.018001 C 0.726661 1.550493 0.117868 H 1.433919 1.461328 0.707345 C 0.177746 3.012158 0.040106 H 0.475981 3.096799 0.837238 C 0.549219 3.447172 1.281995 H 0.067776 3.443573 2.176935 O 1.407236 1.306604 1.345487 O 1.284689 3.908877 0.125021 C 2.765214 1.776419 1.429205 C 1.683768 4.095036 1.488896 C 3.474811 0.977342 2.49447 7 C 3.289263 1.273045 3.851205 C 4.318233 0.084663 2.144170 C 3.926892 0.521414 4.839061 H 2.642468 2.101191 4.132335 C 4.963761 0.835201 3.129497 H 4.470584 0.314196 1.092468 C 4.767159 0. 535501 4.479295 H 3.776241 0.764626 5.887937 H 5.623845 1.650226 2.842953 H 5.271387 1.116869 5.247122 C 3.061649 4.706887 1.523170 C 3.273877 6.002833 1.033765 C 4.146068 3.981852 2.031672 C 4.548790 6.566506 1.054292 H 2.435292 6.565416 0.630621 C 5.422854 4.549033 2.058062 H 3.990183 2.972804 2.407830 C 5.626572 5.840223 1.569730 H 4.702996 7.572460 0.672184 H 6.256886 3.978491 2.458058 H 6.620008 6.281067 1.589668 H 3.259247 1.642753 0.460608

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299 H 2.772935 2.845641 1.669377 H 0.947968 4.748962 1.986541 H 1.694807 3.139955 2.029989 C 5.201444 3.161845 0.134540 O 6.144403 2.639816 0.686131 C 5.242589 3.635813 1.302235 H 4.896536 2.831792 1.966008 H 4.637542 4.526457 1.490082 H 6.283737 3.841173 1.556647 C 1.430886 0.563601 1.088357 C 1.544313 0.682 689 2.059799 H 1.194194 1.414983 1.728532 H 2.398460 0.694844 0.600194 H 1.147663 0.427072 3.048115 C 2.912785 1.312719 2.157272 H 2.925315 2.100283 2.918085 H 3.230343 1.740318 1.210807 O 3.920791 0.307067 2.447130 C 4.157885 0.163519 3.699338 O 4.765860 1.203777 3.817447 C 3.692807 0.661548 4.883637 H 2.601369 0.745878 4.913577 H 4.106358 1.675555 4.844608 H 4.035261 0.167248 5.792921 17 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.94761960000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.87453567000 a.u Ru 0.064964 1.257896 0.982043 O 0.526954 1.563029 2.949114 O 1.435953 0.340 842 2.293976 N 0.650273 3.855881 0.128029 N 2.205083 2.588315 1.025187 C 1.116395 2.576145 0.199473 C 1.344236 4.795956 1.013460 C 0.717126 4.083040 0.349923 C 1.722976 3.979640 0.831184 C 3.167222 4.114801 0.313762 C 3.329487 5.478546 0.389010 C 2.337542 5.573683 1.567221 C 0.890083 5.457928 1.035549 C 2.624687 4.429804 2.561621 C 2.454155 3.056453 1.859077 C 1.004992 2.969368 1.360827 C 3.444338 2.970528 0.679909 C 2.817463 1.492576 1.736287 C 2.136220 0.958526 2.854870 C 2.760813 0.047676 3.596140 C 0.778051 1.466180 3.289970 C 2.523653 3.951107 1.515674 C 4.133495 1.088726 1.438680 C 4.040681 0.518073 3.283757 C 4.708674 0.069887 2.207990 C 4.979606 1.720782 0.354402 C 4.711497 1.591083 4.106558 H 0.316809 3.095656 2.232573 H 1.668790 5.685384 0.465329 H 0.687768 5.122123 1.829997 H 1.587885 3.011810 1.330609 H 1.515258 4.763989 1.572113 H 3.859115 4.048451 1.163054 H 3.153080 6.296310 0.324071 H 4.357683 5.592440 0.757133 H 2.45 3140 6.542163 2.070857 H 0.167766 5.552851 1.857827 H 0.687957 6.273647 0.326136 H 1.950354 4.497504 3.426620 H 3.648488 4.521475 2.949792 H 2.646081 2.248822 2.566734 H 3.348201 2.000071 0. 176394 H 4.474017 3.036924 1.056255 H 2.234891 0.467157 4.451089 H 0.739218 2.561677 3.318849 H 0.029187 1.130174 2.629736 H 0.546255 1.102431 4.295256 H 2.614540 3.944094 2.605555 H 3.481399 4.284886 1.100430 H 5.706560 0.278160 1.953705 H 5.960482 1.997012 0.757857 H 5.158149 1.021257 0.470087 H 4.525534 2.623892 0.060634 H 3.981777 2.163110 4.689189 H 5.261916 2.279659 3.459378 H 5.425960 1.150810 4.815304 C 1.619435 3.639658 1.833723 H 1.970083 3.846557 2.843709 C 2.656058 3.911217 0.779172 H 2.801258 4.994532 0.659594 H 2.390304 3.492302 0.194874 N 1.48163 8 0.755616 3.004156 O 2.485499 0.947131 3.689487 O 3.885139 3.326450 1.259250 C 0.324489 0.387192 0.158913 H 0.748348 0.224967 1.146361 C 0.801164 1.413326 0.249461 H 1.430453 1.373177 0.640 598 C 0.332040 2.893245 0.371795 H 0.321694 3.112474 0.479390 C 0.365359 3.206128 1.667114 H 0.258905 3.078520 2.548255 O 1.568240 1.013581 1.389597 O 1.487954 3.739119 0.300786 C 2.981089 1.196125 1.269319 C 1.771868 4.228523 1.020220 C 3.676055 0.538066 2.438671 C 3.102886 0.534274 3.717199 C 4.937696 0.044573 2.264257 C 3.777009 0.041622 4.795085

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300 H 2.123032 0.979065 3.858810 C 5.617364 0.613467 3.343255 H 5.392844 0.050890 1.276058 C 5.037622 0.615433 4.613153 H 3.318555 0.038453 5.781020 H 6.596461 1.059951 3.189264 H 5.562721 1.061183 5.453949 C 3.225838 4.620 165 1.109468 C 3.753124 5.600605 0.257249 C 4.066935 4.005146 2.044759 C 5.097267 5.961289 0.340012 H 3.105531 6.073102 0.476996 C 5.412342 4.372648 2.133681 H 3.667799 3.236488 2.703471 C 5.929826 5.349472 1.282087 H 5.496321 6.721386 0.326923 H 6.054565 3.890537 2.866097 H 6.976865 5.633831 1.349619 H 3.334311 0.752113 0.326505 H 3.212134 2.268011 1.232195 H 1.120287 5.095768 1.218583 H 1.543706 3.467090 1.774674 C 5.043469 3.355839 0.545397 O 6.041804 2.918860 1.075399 C 5.024435 3.879929 0.874077 H 4.723296 3.079533 1.563379 H 4.352751 4.730293 1.017729 H 6.042591 4.170431 1.137577 C 1.481512 0.583578 0.899940 C 1.530016 0.478071 2.074285 H 1.317202 1.534774 1.405095 H 2.432395 0.558207 0.367462 H 1.102382 0.045013 2.980800 C 2.874450 1.113783 2.332814 H 2.834616 1.757682 3.218028 H 3.211121 1.707566 1.488109 O 3.899766 0.097853 2.486136 C 4.082796 0.599823 3.639705 O 4.718082 1.628688 3.592484 C 3.524556 0.028617 4.928401 H 2.42 9611 0.010270 4.917795 H 3.877268 0.995204 5.095440 H 3.857638 0.664416 5.748908 18 CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.92774141000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.86162679000 a.u Ru 1 .727507 0.197331 0.480674 O 2.038266 2.185156 3.077917 O 0.491139 1.422018 1.695797 N 3.333775 0.120537 1.944465 N 2.860957 1.983023 1.557137 C 2.695584 0.716106 1.091689 C 3.794117 0.547000 3.168083 C 3.037032 1.557274 1.835128 C 1.734220 1.893839 2.606201 C 1.370834 3.376800 2.405373 C 2.523785 4.258481 2.926022 C 3.816580 3.923317 2.154110 C 4.179061 2.437147 2.385856 C 3.5858 74 4.187718 0.651169 C 2.436801 3.289391 0.122066 C 2.862979 1.815658 0.319081 C 1.150054 3.629197 0.900713 C 2.307681 3.205399 1.046450 C 1.116270 3.690634 1.632015 C 0.596164 4.904044 1.17 6922 C 0.408470 2.931614 2.733279 C 3.738378 2.023576 2.748924 C 2.992008 3.953795 0.073050 C 1.229002 5.652644 0.175797 C 2.426106 5.165289 0.350559 C 4.311606 3.512857 0.514336 C 0.629718 6.950167 0.314027 H 3.868095 1.735559 0.113412 H 4.800657 0.224643 3.446011 H 3.118037 0.328860 4.006147 H 0.915645 1.255383 2.246323 H 1.862238 1.679065 3.676930 H 0.452276 3.597527 2.962351 H 2.669883 4.094998 4.003365 H 2.275099 5.320193 2.795088 H 4.639971 4.550441 2.520435 H 5.119028 2.186207 1.875460 H 4.332583 2.260286 3.461235 H 4.506471 3.992897 0.083808 H 3.337644 5.247558 0.498005 H 2.297009 3.490798 0.943452 H 0.314851 3.021299 0.532502 H 0.877573 4.680271 0.731261 H 0.321377 5.281314 1.624078 H 1.037320 2.824387 3.625795 H 0.119204 1.921079 2.423750 H 0.499332 3.460967 3.037940 H 3.321556 2.678521 3.517931 H 4.726826 2.412320 2.470578 H 2.951868 5.747703 1.104382 H 4.940561 4.381784 0.733628 H 4.185395 2.966470 1.455202 H 4.866982 2.85 7942 0.162369 H 0.204899 7.532377 0.511226 H 0.181807 6.765528 1.030084 H 1.376595 7.570766 0.818883 C 4.387143 2.149803 0.892710 H 4.474162 2.925097 1.654079 C 5.578026 1.228421 0.861023 H 5.502516 0.496267 1.672961 H 5.660785 0.683051 0.076997

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301 N 0.860310 2.207041 2.689410 O 0.015980 2.914652 3.188526 O 6.784017 1.958100 1.171895 C 0.274990 1.378086 0.668666 H 0.110240 2.040946 0.173693 C 1.470592 0.467269 0.557136 H 1.357226 0.361116 1.262826 C 2.804073 1.207798 0.932885 H 2.570967 1.835240 1.810253 C 3.261303 2.125463 0.169101 H 2.514471 2.884859 0.402110 O 1.45 7203 0.037630 0.780577 O 3.806611 0.264621 1.297045 C 2.289708 1.184033 1.003130 C 3.722604 0.178090 2.664593 C 2.353788 1.487734 2.480690 C 2.424702 0.456931 3.427706 C 2.412852 2.815727 2. 921378 C 2.545615 0.751275 4.786730 H 2.386116 0.573920 3.090064 C 2.543614 3.111124 4.280191 H 2.358861 3.624318 2.195755 C 2.607144 2.078747 5.217788 H 2.599141 0.058053 5.510638 H 2.590436 4.147326 4.604823 H 2.705182 2.306427 6.275871 C 4.455336 1.485798 2.815023 C 5.853106 1.514185 2.903627 C 3.742983 2.691868 2.849740 C 6.532951 2.727229 3.012224 H 6.410337 0.579588 2.895600 C 4.422743 3.906388 2.964039 H 2.655492 2.682718 2.803585 C 5.816732 3.926649 3.041349 H 7.617498 2.737229 3.081371 H 3.860169 4.835369 2.998607 H 6.344179 4.872588 3.132216 H 1.8899 19 2.043212 0.445961 H 3.294540 0.987697 0.614058 H 4.154417 0.601121 3.311394 H 2.673737 0.311990 2.955901 C 7.468862 2.648895 0.219348 O 8.414470 3.318481 0.560169 C 7.025539 2.512834 1.22 6482 H 5.964658 2.749540 1.352682 H 7.179252 1.486960 1.581584 H 7.631662 3.190574 1.828186 C 0.430311 1.577415 1.810087 C 3.021111 0.220888 1.706722 H 0.217200 1.016003 2.715657 H 1.145565 2.389100 1.885121 H 2.682569 0.497473 2.716391 C 4.519437 0.114275 1.653428 H 4.799322 0.933417 1.827771 H 4.925966 0.404409 0.682507 O 5.145876 0.985069 2.609926 C 5.358638 0.618569 3.914543 O 5.750996 1.466204 4.678085 C 5.124120 0.826831 4.305550 H 4.098565 1.156462 4.108689 H 5.796090 1.495463 3.753790 H 5.336148 0.918056 5.371132 TS16E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93831302000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.86186948000 a.u Ru 1.711839 0.544505 0.620138 O 2.763654 0.732188 2.842430 O 0.665238 0.266874 2.531567 N 2.627331 2.470449 1.339645 N 3.2 97189 0.551029 2.152714 C 2.680807 1.141939 1.079701 C 3.036908 2.824597 2.700792 C 1.886806 3.361886 0.441898 C 0.449689 3.619207 0.958716 C 0.322752 4.472481 0.067438 C 0.395600 5.823269 0 .258003 C 1.830078 5.571192 0.766677 C 2.598719 4.727584 0.276649 C 1.765137 4.821537 2.114584 C 1.052728 3.456457 1.924999 C 1.879891 2.634346 0.916541 C 0.377060 3.716597 1.410564 C 3.897182 0.751287 2.223457 C 3.348194 1.712227 3.092330 C 3.976296 2.960185 3.189410 C 2.124668 1.421935 3.932208 C 3.761370 1.549395 3.144096 C 5.091260 1.011688 1.516009 C 5.133909 3.265213 2.470082 C 5.681072 2.271045 1.649829 C 5.728571 0.031929 0.625806 C 5.770876 4.631915 2.555738 H 2.922330 2.633824 1.275286 H 3.683650 3.705971 2.711162 H 2.156920 3.035680 3.323054 H 0.0632 73 2.665357 1.121615 H 0.486276 4.141749 1.925490 H 1.341267 4.645601 0.305251 H 0.419507 6.377466 0.691091 H 0.153335 6.445752 0.977490 H 2.349016 6.529478 0.900450 H 3.634773 4.562844 0.04 7827 H 2.634750 5.272793 1.231505 H 2.776045 4.662804 2.512956 H 1.223632 5.432567 2.850694 H 1.007106 2.945764 2.892266 H 0.910254 2.767661 1.287457

PAGE 309

302 H 0.938360 4.305774 2.149260 H 3.545734 3.712121 3.847305 H 1.610533 2.348689 4.205486 H 2.395701 0.918522 4.870395 H 1.414133 0.770114 3.415865 H 3.501890 1.237027 4.159070 H 4.852947 1.651192 3.086856 H 6.593655 2.482213 1.096557 H 5.935460 0.961963 1.168668 H 6.677586 0.335035 0.224215 H 5.085285 0.297658 0.220940 H 5.487699 5.249185 1.693455 H 6.864433 4.564528 2.560813 H 5.458167 5.164678 3.459443 N 1.626142 0.51 2693 3.368415 O 1.428674 0.517955 4.572851 C 3.280121 2.774503 0.965652 H 4.126366 2.624273 0.299673 C 3.500551 3.588045 2.206624 H 2.556341 3.761018 2.729896 H 3.944865 4.563049 1.981013 O 4.320858 2.876593 3.165007 C 0.197905 0.047450 0.396518 H 0.183794 0.094796 1.483153 C 1.237370 0.037013 0.140711 H 1.286601 0.658120 1.042496 C 1.838194 1.351799 0.538768 H 1.105594 1.855847 1.188254 C 2.109910 2.204984 0.671697 H 1.266933 2.329901 1.351121 O 1.973790 0.638850 0.923325 O 3.041936 1.179523 1.275100 C 3.142932 1.385794 0.540425 C 2.850743 1.064450 2.691652 C 3.913522 1.756991 1.783048 C 4.225147 3.090883 2.066515 C 4.364767 0.755307 2.654242 C 4.984234 3.419519 3.193141 H 3.877789 3.877602 1.399474 C 5.121612 1.077941 3.779364 H 4.115673 0.281749 2.454434 C 5.434770 2.413895 4.049597 H 5.221507 4.460235 3.399640 H 5.475551 0.278875 4.424682 H 6.029340 2.668521 4.923379 C 4.193872 0.887860 3.353458 C 4.488561 0.272137 4.076914 C 5.166 682 1.892645 3.256616 C 5.729882 0.426858 4.699123 H 3.740411 1.057384 4.157324 C 6.408510 1.738860 3.870399 H 4.944490 2.797026 2.695639 C 6.692381 0.577621 4.595493 H 5.943689 1.332162 5.2 60916 H 7.154565 2.525075 3.788826 H 7.659137 0.459009 5.077524 H 3.758873 0.773383 0.126310 H 2.840438 2.289070 0.009048 H 2.189634 0.221372 2.929702 H 2.354822 1.979244 3.055679 C 5.673395 3.000998 3.225755 O 6.279321 2.302536 4.004376 C 6.354532 4.024044 2.333661 H 6.040698 5.043276 2.586974 H 6.130122 3.858784 1.274681 H 7.429750 3.936604 2.490610 C 1.442034 1.719894 0.042112 C 2.564692 1.490514 0.790556 H 1.602337 1.847250 1.104983 H 0.616546 2.284340 0.376973 H 3.530549 1.454666 0.300246 C 2.614651 2.126931 2.159233 H 3.362971 1.637878 2.784904 H 1.640854 2.0 80008 2.656729 O 2.975384 3.513792 1.942204 C 3.296541 4.336577 2.979303 O 3.573291 5.487459 2.736942 C 3.295884 3.752886 4.379631 H 4.072799 2.987080 4.486689 H 2.339814 3.279144 4.626680 H 3.494726 4.561507 5.083336 TS17E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.95611186000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.88664101000 a.u Ru 1.490505 0.692190 0.610877 O 1.431796 2.916147 2.08857 2 O 0.147216 1.410690 2.209857 N 3.527395 1.045558 1.403544 N 3.395834 1.128278 1.143506 C 2.849754 0.058289 0.753350 C 4.434918 0.543185 2.439047 C 2.929763 2.380508 1.413086 C 1.915199 2.507383 2.582806 C 1.198913 3.868903 2.523795 C 2.248053 4.995167 2.624377 C 3.251551 4.871997 1.458807 C 3.977420 3.508842 1.537253 C 2.487837 4.979073 0.123812 C 1.434741 3.841502 0.015597 C 2.193007 2.505709 0.070622 C 0.439160 3.967060 1.186946 C 2.899943 2.461307 0.930995 C 1.890459 2.940013 1.798707 C 1.402580 4.234635 1.608251 C 1.361859 2.094456 2.937141 C 4.547988 0.93 7819 2.052818 C 3.481077 3.300329 0.035083

PAGE 310

303 C 1.915061 5.071452 0.605707 C 2.956579 4.592517 0.190026 C 4.666031 2.888379 0.882220 C 1.377200 6.472595 0.430230 H 2.942501 2.479767 0.755705 H 5.397880 1.060089 2.412545 H 3.999406 0.677085 3.438713 H 1.185317 1.691054 2.511959 H 2.439825 2.398608 3.542563 H 0.491639 3.939119 3.359647 H 2.774180 4.938227 3.587977 H 1.754254 5.975269 2.588341 H 3.997128 5.674925 1.525648 H 4.716968 3.417659 0.730283 H 4.520408 3.429783 2.490471 H 3.184823 4.925695 0.723343 H 1.981514 5.951723 0.058396 H 0.917724 3.953601 0.937488 H 0.32 3707 3.180878 1.128815 H 0.088881 4.927305 1.119655 H 0.610174 4.595948 2.259868 H 0.591882 2.638217 3.489438 H 2.162095 1.837022 3.643930 H 0.930089 1.149812 2.588104 H 4.476424 1.614689 2. 907912 H 5.482975 1.155305 1.520910 H 3.385550 5.238777 0.953469 H 5.544446 3.495686 0.628619 H 4.466717 3.043078 1.948797 H 4.935266 1.839070 0.739499 H 0.289740 6.498622 0.557500 H 1.618220 6.874472 0.559160 H 1.804400 7.154585 1.177284 N 0.295502 2.616111 2.482244 O 0.426669 3.373861 3.137054 C 3.714270 3.051201 0.500222 H 4.603028 2.654334 0.014647 C 3.968132 4.112894 1.533687 H 4.337216 5.030432 1.059913 H 4.745130 3.788649 2.236627 O 2.787846 4.527591 2.239246 C 0.127557 0.761977 0.320023 H 0.311134 1.434614 0.514537 C 1.349866 0.385251 0.387189 H 1.4797 75 0.456387 1.069115 C 2.282305 1.531421 0.895365 H 1.790741 2.004744 1.763667 C 2.514214 2.589906 0.148874 H 1.616746 2.988539 0.617421 O 1.697139 0.018663 0.940608 O 3.533261 0.995446 1.31 3827 C 2.773287 0.948844 1.016906 C 3.524880 0.464379 2.644764 C 2.919512 1.461204 2.433691 C 4.009672 2.286185 2.746519 C 2.000483 1.149959 3.441765 C 4.173081 2.795759 4.033630 H 4.734632 2.532402 1.972989 C 2.166074 1.657382 4.734585 H 1.160938 0.504451 3.208569 C 3.249881 2.482337 5.035470 H 5.023113 3.435683 4.256333 H 1.444744 1.403211 5.507739 H 3.377634 2.876466 6.040238 C 4.819737 0.268510 2.887053 C 4.839065 1.666653 2.953477 C 6.020242 0.439289 3.032163 C 6.040777 2.346286 3.167306 H 3.909952 2.220390 2.837986 C 7.221164 0.237941 3.240495 H 6.009411 1.52 5673 2.981161 C 7.232708 1.634121 3.309990 H 6.043546 3.431720 3.221897 H 8.146613 0.320861 3.354334 H 8.167551 2.162778 3.477852 H 3.708416 0.478579 0.688027 H 2.578653 1.788267 0.330720 H 2.680654 0.223022 2.782395 H 3.402819 1.296887 3.357521 C 2.319045 3.847390 3.317589 O 1.259790 4.199246 3.792830 C 3.133937 2.698450 3.872230 H 4.131563 3.024393 4.186460 H 3.252089 1.909520 3.122396 H 2.604713 2.295640 4.735640 C 0.832843 1.280225 1.640232 C 2.200112 0.552072 1.996216 H 1.082581 2.330305 1.470845 H 0.159558 1.160454 2.490166 H 3.058673 1.149808 1.702795 C 2.36 1251 0.096931 3.431622 H 3.202054 0.605002 3.503350 H 1.461112 0.392181 3.802248 O 2.666565 1.287230 4.199599 C 2.804928 1.247279 5.554827 O 3.092665 2.266797 6.135264 C 2.579564 0.080845 6.251483 H 3.250599 0.857322 5.868277 H 1.554583 0.438152 6.102152 H 2.759762 0.060023 7.317409 TS18E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.94339454000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.8 6075229000 a.u Ru 1.741370 0.438337 0.415405 O 0.521415 1.702302 1.098785 O 0.792840 2.371015 0.941566 N 3.726588 0.838685 1.263098

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304 N 2.585544 2.506692 0.424764 C 2.690142 1.142804 0.435852 C 4 .225408 1.989683 2.020504 C 4.000903 0.555513 1.620647 C 3.311212 0.935593 2.956165 C 3.572741 2.420950 3.282965 C 5.089149 2.676428 3.383183 C 5.752813 2.318183 2.038208 C 5.521214 0.815951 1.758008 C 5.134444 3.180688 0.913890 C 3.608925 2.899460 0.807145 C 3.459235 1.398980 0.448270 C 2.974469 3.290866 2.161364 C 1.710739 3.351622 0.337728 C 0.530760 3.827131 0.276210 C 0.309999 4.672699 0.453519 C 0.175538 3.459780 1.701322 C 3.657870 3.155948 1.207362 C 2.086317 3.796017 1.619680 C 0.003531 5.073549 1.759241 C 1.205723 4.634840 2.317307 C 3.421759 3.457493 2.246561 C 0.921319 5.996367 2.518822 H 4.160588 1.231134 0.380416 H 5.317288 1.997885 2.067718 H 3.835698 1.976989 3.047889 H 2.234322 0.750176 2.872155 H 3.696300 0.301984 3.768386 H 3.09 2395 2.667805 4.239023 H 5.528924 2.077116 4.193491 H 5.275505 3.730854 3.627844 H 6.833078 2.507363 2.095381 H 6.027401 0.508848 0.832746 H 5.953690 0.225035 2.579276 H 5.629617 2.963818 0. 043005 H 5.308983 4.244358 1.130083 H 3.184242 3.518847 0.007332 H 1.890040 3.176658 2.147421 H 3.183508 4.351001 2.363690 H 1.228591 5.024773 0.009660 H 0.746210 3.963671 2.002140 H 0.967022 3.759569 2.399882 H 0.030706 2.381330 1.834047 H 3.251918 3.960423 1.826129 H 4.405183 3.590094 0.529122 H 1.480009 4.961048 3.319051 H 4.087047 4.330979 2.222367 H 3.307291 3.177728 3.29990 1 H 3.932127 2.641015 1.731424 H 1.969253 5.796568 2.272638 H 0.794371 5.891435 3.601463 H 0.724985 7.046747 2.265328 N 0.309485 2.614446 0.229770 O 0.314243 3.636783 0.477585 C 4.743357 1. 645517 0.716898 H 5.429309 0.812206 0.853245 C 5.382709 2.939999 0.296842 H 5.968680 3.365388 1.120549 H 6.083271 2.768834 0.529522 O 4.445164 3.973562 0.041201 C 0.387752 0.607895 0.701680 H 0.298729 1.477456 0.063633 C 1.617539 0.229442 0.393721 H 1.432115 1.292200 0.579446 C 2.821655 0.149881 1.327900 H 2.428041 0.242455 2.354397 C 3.440306 1.461539 0.926235 H 2.742723 2.287135 0.802708 O 1.937206 0.008749 0.970740 O 3.807908 0.874774 1.297736 C 2.698534 1.047570 1.605368 C 3.581503 1.934878 2.233253 C 2.756395 0.764356 3.086295 C 3.980380 0.536828 3.724571 C 1.579410 0.739048 3.848587 C 4.034797 0.285987 5.098745 H 4.899095 0.563867 3.142245 C 1.630241 0.483760 5.218206 H 0.630839 0.933576 3.356655 C 2.858230 0.255416 5.847545 H 4.994017 0.115 701 5.581174 H 0.711848 0.470626 5.800049 H 2.895991 0.060352 6.916269 C 4.497191 3.085038 1.900634 C 4.047055 4.134421 1.089511 C 5.815730 3.104705 2.371181 C 4.901450 5.186728 0.756284 H 3.023735 4.126920 0.719924 C 6.672094 4.154959 2.038824 H 6.170328 2.293085 3.002634 C 6.215119 5.198476 1.230246 H 4.540041 5.997243 0.129180 H 7.692551 4.161820 2.412992 H 6.879657 6.019426 0.973774 H 3.706939 1.096020 1.181353 H 2.204976 2.011861 1.420651 H 2.535622 2.269435 2.188164 H 3.769061 1.562259 3.252778 C 3.883775 4.062713 1.277383 O 3.051949 4.926252 1.458815 C 4.311806 3.088335 2.352521 H 5.391522 3.123993 2.533289 H 4.045223 2.064890 2.069206 H 3.788699 3.350547 3.271995 C 0.187973 0.677623 1.966349 C 2.384721 0.036076 2.127767 H 0.621242 1.610009 2.308256 H 0.118458 0.012676 2.748620

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305 H 2.778817 0.919755 2.486661 C 2.463573 1.080007 3.204527 H 3.508864 1.433793 3.225363 H 1.817657 1.937287 3.000114 O 2.129840 0.470640 4.470499 C 2.12 0908 1.185982 5.633194 O 1.820687 0.618076 6.654784 C 2.487547 2.656001 5.564138 H 3.487367 2.802320 5.140569 H 1.782321 3.212289 4.936256 H 2.462008 3.059545 6.576512 11E CB B3LYP/SDD/6 31G(d) SCF e nergy in gas p hase: 2839.95816022000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.88803799000 a.u Ru 1.753224 0.405363 0.691497 O 2.764018 0.108354 3.389548 O 0.782653 0.222841 2.510059 N 2.572810 2.597665 1.002966 N 2.899076 0.850437 2.278227 C 2.523849 1.245723 1.021809 C 2.790088 3.203648 2.319167 C 2.034673 3.306747 0.159435 C 0.532202 3.643992 0.037345 C 0.027008 4.305312 1.237696 C 0.761 823 5.595806 1.535342 C 2.253693 5.255261 1.733626 C 2.809283 4.614078 0.442663 C 2.400178 4.266647 2.907627 C 1.608005 2.963587 2.611426 C 2.211388 2.335729 1.342760 C 0.120918 3.317630 2.4 11534 C 3.335495 0.450547 2.704933 C 2.538505 1.193406 3.593315 C 3.001845 2.446803 4.018472 C 1.232071 0.665462 4.141657 C 3.285379 1.999734 3.130135 C 4.612675 0.917045 2.316979 C 4.233092 2.959534 3.609493 C 5.030050 2.168618 2.771352 C 5.522889 0.093625 1.432480 C 4.696420 4.330070 4.042530 H 3.288723 2.153335 1.504650 H 3.521689 4.014683 2.273702 H 1.849847 3.609867 2.715139 H 0.028706 2.727762 0.261240 H 0.413602 4.320710 0.895723 H 1.086300 4.539938 1.081789 H 0.642310 6.313512 0.711265 H 0.366406 6.079260 2.438763 H 2.819386 6.171727 1.947136 H 3.879767 4.3 92389 0.550261 H 2.700257 5.317512 0.395813 H 3.458977 4.031004 3.081039 H 2.019872 4.724233 3.831361 H 1.729619 2.286997 3.458894 H 0.457790 2.408024 2.215582 H 0.279571 3.763652 3.332432 H 2.379554 3.032371 4.692282 H 0.491097 1.467478 4.230677 H 1.372775 0.250165 5.148924 H 0.812742 0.126438 3.517317 H 2.818236 1.922344 4.115920 H 4.373721 2.013173 3.268853 H 6.003185 2.540941 2.458988 H 5.827668 0.840938 1.920257 H 6.433544 0.651503 1.196191 H 5.041534 0.181874 0.488316 H 4.589006 5.054352 3.225093 H 5.753907 4.322574 4.330054 H 4.115389 4.700524 4.892996 N 1.567733 0.215706 3.562553 O 1.093495 0.534677 4.647192 C 3.638200 1.380406 2.299378 H 4.439163 1.698922 1.636743 C 4.001235 0.961872 3.693890 H 3.101973 0.819481 4.299432 H 4.628192 1.708329 4.192662 O 4.655437 0.330527 3.717606 C 0.299296 0.497918 0.359413 H 0.257675 0.227747 1.415270 C 1.105274 0.605442 0.225493 H 1.033088 0.844113 1.293269 C 1.935472 1.745070 0.464736 H 1.27 1942 2.624386 0.555271 C 2.383141 1.350797 1.846541 H 1.586557 1.013637 2.508727 O 1.719618 0.669725 0.052702 O 3.075674 2.121192 0.298834 C 2.792977 0.946018 0.969146 C 2.811657 3.038925 1. 360702 C 3.516178 2.200879 0.545475 C 3.738423 3.240428 1.456050 C 4.033912 2.315724 0.752540 C 4.470016 4.371176 1.080767 H 3.343322 3.162262 2.466730 C 4.765819 3.440953 1.130381 H 3.866025 1.518957 1.469666 C 4.985826 4.472406 0.212190 H 4.637399 5.168923 1.800261 H 5.180234 3.489909 2.133313 H 5.561080 5.347940 0.502620 C 4.122576 3.497271 1.950957 C 4.407536 3.298508 3.305208 C 5.069674 4.143830 1.144587 C 5.614691 3.743378 3.850477 H 3.681698 2.792478 3.937553 C 6.277285 4.582966 1.684050

PAGE 313

306 H 4.854862 4.296258 0.089983 C 6.551803 4.385311 3.040821 H 5.82234 2 3.583225 4.905000 H 7.004070 5.083481 1.049399 H 7.492162 4.730409 3.462336 H 3.486434 0.097905 0.978995 H 2.384377 1.058660 1.984271 H 2.188816 2.574999 2.138291 H 2.248656 3.897681 0.956 736 C 6.005426 0.484552 3.670022 O 6.453859 1.606635 3.640350 C 6.883492 0.754494 3.678203 H 6.781717 1.306888 4.619492 H 6.634924 1.438326 2.859970 H 7.918060 0.427751 3.571865 C 1.244588 1.737900 0.105605 C 2.668321 1.374647 0.479737 H 1.423100 2.224313 1.067742 H 0.758828 2.426896 0.589755 H 3.430906 1.434988 0.290777 C 3.099562 2.212220 1.665307 H 3.966423 1.761201 2.155545 H 2.299415 2.333039 2.398343 O 3.454855 3.509391 1.121171 C 3.927396 4.511134 1.913138 O 4.214079 5.566603 1.398700 C 4.064581 4.237155 3.398478 H 4.750307 3.404410 3.589817 H 3.101986 3.969 657 3.848197 H 4.448859 5.138526 3.876400 11E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.96199265000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.89169707000 a.u Ru 1.693745 0.704411 0.282118 O 0.277498 2.948498 0.726607 O 0.829840 2.519616 1.120277 N 3.746687 0.540178 1.348089 N 2.953366 2.197257 0.160581 C 2.798987 0.870702 0.429313 C 4.469168 1.693566 1.893154 C 3.661483 0.756429 2.015512 C 2.851354 0.640678 3.334963 C 2.688144 2.029362 3.980818 C 4.080507 2.624082 4.274963 C 4.874841 2.749323 2.958688 C 5.055555 1.347225 2.334962 C 4.103577 3.662270 1.982747 C 2.703855 3.057425 1.680611 C 2.933617 1.683359 1.033186 C 1.919386 2.936956 3.003339 C 2.124417 3.076544 0.619391 C 1.009497 3.674694 0.012672 C 0.212535 4.551443 0.726762 C 0.681254 3.399169 1.464108 C 4.096340 2.791793 0.889423 C 2.488309 3.429528 1.930584 C 0.508334 4.864470 2.061568 C 1.650263 4.305819 2.636700 C 3.760799 2.949239 2.595222 C 0.372024 5.820097 2.832934 H 3.581496 1.82 2085 0.130506 H 5.545829 1.507702 1.934686 H 4.121143 1.926108 2.908455 H 1.868491 0.205788 3.112181 H 3.365372 0.040596 4.027324 H 2.123468 1.926420 4.916400 H 4.625303 1.987975 4.987108 H 3.975378 3.611246 4.744034 H 5.864760 3.177817 3.162293 H 5.649433 1.405766 1.412764 H 5.600009 0.697446 3.035406 H 4.671283 3.789369 1.050522 H 3.984253 4.662154 2.421926 H 2.169780 3.714420 0.990912 H 0.920497 2.536652 2.807966 H 1.785769 3.935672 3.440305 H 0.654069 5.000809 0.247659 H 0.192824 3.977860 1.771509 H 1.516444 3.673987 2.121720 H 0.465798 2.340211 1.645823 H 3.79 8090 3.729373 1.365778 H 4.912280 3.010081 0.188894 H 1.911849 4.561648 3.661857 H 4.442191 3.792987 2.764526 H 3.555259 2.503305 3.575065 H 4.293190 2.208418 1.993946 H 1.428897 5.663598 2. 592476 H 0.241878 5.703869 3.913792 H 0.136185 6.862751 2.581809 N 0.017163 3.260608 0.450375 O 0.526466 4.219123 1.035173 C 4.257759 2.026460 0.893496 H 5.025110 1.277560 1.076557 C 4.767883 3.399005 0.551785 H 5.219896 3.872562 1.431775 H 5.554502 3.338472 0.209813 O 3.738573 4.314431 0.144427 C 0.007671 0.376398 0.625336 H 0.045917 1.403045 0.272291 C 1.376974 0.198466 0.35528 4 H 1.363111 1.285983 0.440024 C 2.487690 0.303217 1.341250 H 2.059159 0.333620 2.357361 C 2.973050 1.684582 0.989946 H 2.195544 2.425878 0.818759 O 1.682398 0.167356 0.989285 O 3.587652 0.602575 1.337240

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307 C 2.628321 0.679968 1.647005 C 3.439993 1.713876 2.230135 C 2.834195 0.192753 3.063059 C 4.077081 0.369749 3.685000 C 1.798937 0.411048 3.788741 C 4.281068 0.036668 5.005088 H 4.891390 0.831202 3.130141 C 2.003843 0.827939 5.104913 H 0.837647 0.562939 3.308439 C 3.244420 0.640479 5.719353 H 5.251900 0.110692 5.471482 H 1.192387 1.300506 5.653238 H 3.402328 0.96 4494 6.744756 C 4.515357 2.726606 1.928706 C 4.200259 3.918449 1.264896 C 5.846178 2.473974 2.286777 C 5.202990 4.844436 0.967134 H 3.168500 4.123807 0.987204 C 6.848313 3.395797 1.985971 H 6.094396 1.549732 2.803795 C 6.526994 4.584685 1.324821 H 4.947165 5.768643 0.455811 H 7.877287 3.191164 2.270655 H 7.306227 5.306564 1.093856 H 3.582414 0.684270 1.108792 H 2.242550 1.710214 1.644750 H 2.452981 2.180151 2.112360 H 3.516180 1.349222 3.267640 C 3.300613 4.376338 1.141699 O 2.366367 5.110588 1.385177 C 3.996018 3.542903 2.195828 H 5.054579 3.811244 2.286443 H 3.93 1916 2.476862 1.956420 H 3.500955 3.722880 3.149838 C 0.578261 0.258885 2.090969 C 2.095396 0.186076 2.169352 H 0.533008 1.260754 2.527528 H 0.015964 0.448375 2.672253 H 2.755322 0.666074 2. 308357 C 2.407887 1.252498 3.197853 H 3.440892 1.602174 3.067566 H 1.729421 2.101005 3.112689 O 2.288425 0.618454 4.495717 C 2.340944 1.337817 5.651417 O 2.269587 0.746694 6.702419 C 2.476029 2.845077 5.545127 H 3.354795 3.133692 4.958183 H 1.599766 3.286458 5.056694 H 2.564547 3.248940 6.553914 11E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.95572930000 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 2838.88474803999 a.u Ru 1.775158 0.295577 0.775557 O 0.187282 2.331981 2.632950 O 0.827206 0.217704 2.684940 N 2.858519 2.624447 0.543250 N 3.050772 1.054251 2.056401 C 2.650479 1.301174 0.772093 C 3.206508 3.377397 1.751718 C 2.282790 3.226507 0.660384 C 0.843530 3.743710 0.388968 C 0.217857 4.272044 1.694174 C 1.086891 5.419036 2.248735 C 2.513572 4.898502 2.523107 C 3.139937 4.392842 1.203586 C 2.448783 3.745458 3.545994 C 1.575140 2.588588 2.990704 C 2.234659 2.092771 1.694778 C 0.154855 3.121256 2.716926 C 3.248186 0.210356 2.708889 C 2.312 633 0.634886 3.672764 C 2.519860 1.867059 4.304670 C 1.143187 0.227708 4.091966 C 3.651476 2.250353 2.688069 C 4.426542 0.950430 2.472128 C 3.636680 2.661903 4.032647 C 4.586368 2.174154 3.128412 C 5.538410 0.438144 1.581180 C 3.817588 4.009643 4.690209 H 3.272345 1.759294 1.916320 H 3.996647 4.107242 1.558487 H 2.328070 3.910735 2.139561 H 0.232032 2.929305 0.020060 H 0.87253 2 4.543455 0.364460 H 0.794208 4.635943 1.480073 H 1.118909 6.253090 1.533354 H 0.648282 5.810620 3.176268 H 3.135119 5.711709 2.920120 H 4.169442 4.048029 1.370981 H 3.181881 5.215754 0.475 210 H 3.460649 3.381709 3.773750 H 2.021196 4.108608 4.490772 H 1.529713 1.774661 3.716845 H 0.479904 2.311301 2.340871 H 0.295319 3.472780 3.655319 H 1.790391 2.208780 5.036018 H 0.318824 0.385925 4.468940 H 1.433803 0.901199 4.910296 H 0.764431 0.853188 3.280519 H 3.289698 2.369186 3.712683 H 4.744072 2.146081 2.717700 H 5.479272 2.762124 2.927281 H 6.261508 0.147384 2.165225 H 6.089300 1.269622 1.130503 H 5.173062 0.202748 0.774957 H 3.562758 4.821313 3.996765 H 4.856284 4.166944 5.001397

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308 H 3.178197 4.115159 5.572417 N 0.135616 1.204406 3.181468 O 0.547413 0.981 106 4.180197 C 3.386920 1.447889 2.621000 H 4.232173 1.701525 1.986133 C 3.661623 1.039952 4.038400 H 2.733571 1.007777 4.615815 H 4.344378 1.735472 4.537456 O 4.179842 0.311249 4.127575 C 0.436968 0.598363 0.431841 H 0.463996 0.248324 1.462818 C 1.006660 0.731319 0.033278 H 1.041503 0.986282 1.093756 C 1.799583 1.870334 0.701748 H 1.143635 2.757609 0.737748 C 2.153596 1.489173 2.112683 H 1.306063 1.221581 2.743435 O 1.586886 0.552617 0.184251 O 2.981909 2.190375 0.018391 C 2.721173 0.859535 0.643933 C 2.804653 3.204111 1.024649 C 3.312439 2.176292 0.204618 C 3.540 284 3.204917 1.125948 C 3.694628 2.366734 1.131138 C 4.142874 4.400621 0.723142 H 3.253659 3.066848 2.166290 C 4.297053 3.557234 1.536542 H 3.521982 1.577801 1.856191 C 4.522143 4.578511 0.608248 H 4.317750 5.188858 1.451372 H 4.609117 3.666229 2.571251 H 4.996984 5.505193 0.920819 C 3.969689 3.158372 1.979878 C 3.798480 2.666700 3.280075 C 5.239660 3.590222 1.574494 C 4.88206 8 2.610381 4.160092 H 2.816074 2.331599 3.606385 C 6.322578 3.529998 2.450785 H 5.376538 3.974842 0.566249 C 6.144470 3.039520 3.747530 H 4.737027 2.230223 5.167798 H 7.303240 3.868741 2.126 290 H 6.986851 2.995586 4.433157 H 3.462205 0.058134 0.557532 H 2.403960 0.907040 1.696481 H 1.870066 3.042776 1.572742 H 2.741454 4.183743 0.523980 C 5.508144 0.601503 4.116214 O 5.841693 1.762864 4.151010 C 6.505454 0.543074 4.079676 H 6.451272 1.146359 4.993355 H 6.332260 1.209059 3.228145 H 7.503358 0.111109 4.001985 C 1.430835 1.796520 0.189598 C 2.803174 1.391805 0.522071 H 1.716148 2.184532 1.170057 H 0.948514 2.554495 0.425686 H 3.616753 1.377880 0.197420 C 3.192491 2.230196 1.722892 H 4.060052 1.782615 2.225833 H 2.366435 2.323897 2.421823 O 3.583163 3.527 799 1.210070 C 3.520039 4.657460 1.971108 O 3.871830 5.701096 1.473740 C 3.005917 4.537220 3.392632 H 3.582159 3.804912 3.969288 H 1.958190 4.216379 3.408825 H 3.091562 5.516778 3.863790 TS19 E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93007790000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.85434983000 a.u Ru 1.597108 0.743959 0.602149 O 2.620814 1.508411 2.762427 O 0.525349 0.987732 2.493917 N 2.362709 2.130992 1.828767 N 3.097695 0.102408 2.198346 C 2.518597 0.914140 1.254490 C 2.654224 2.153693 3.265456 C 1.618372 3.189252 1.138149 C 0.145953 3.243389 1.618102 C 0.626650 4.295747 0.798342 C 0.019526 5.680260 1.003435 C 1.489340 5.633439 0.536117 C 2.257151 4.581819 1.370412 C 1.531414 5.256455 0.959468 C 0.889705 3.860116 1.168904 C 1.711459 2.837678 0.358988 C 0.575619 3.912437 0.694214 C 3.804668 1.129772 1.980700 C 3.234557 2.344485 2.405010 C 3.923831 3.534020 2.136864 C 1.921083 2.392950 3.152190 C 3.402729 0.830404 3.451674 C 5.102491 1.098 782 1.425554 C 5.163331 3.543814 1.493495 C 5.752465 2.312093 1.187906 C 5.794266 0.203063 1.080248 C 5.822746 4.835084 1.077197 H 2.769632 2.957028 0.649218 H 3.254649 3.025124 3.539895 H 1.720825 2.183751 3.842021 H 0.317688 2.257668 1.508553 H 0.109083 3.506432 2.684879 H 1.668835 4.321374 1.143449 H 0.034916 5.970614 2.062258 H 0.529718 6.442514 0.434392 H 1.957244 6.615392 0.685677

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309 H 3.314813 4.553428 1.076210 H 2.218325 4.860050 2.433889 H 2.567502 5.249800 1.323480 H 0.991111 6.012186 1.546922 H 0.920044 3.619317 2.235423 H 1.056013 2.940928 0.856127 H 1.134 340 4.648858 1.288730 H 3.466298 4.478789 2.422655 H 1.449249 3.375432 3.051026 H 2.074020 2.220412 4.226312 H 1.216768 1.632294 2.806008 H 3.060184 0.259660 4.319378 H 4.485432 0.976916 3.5 46246 H 6.734637 2.296521 0.720528 H 6.129621 0.731162 1.982469 H 6.682028 0.015425 0.468940 H 5.144068 0.890592 0.529618 H 5.612228 5.028500 0.016646 H 6.911242 4.790643 1.194709 H 5.449517 5.686434 1.655641 N 1.468607 1.405344 3.286264 O 1.231143 1.672842 4.453457 C 3.263273 3.086822 0.317309 H 4.136224 2.814508 0.270768 C 3.434697 4.120170 1.391806 H 2.466351 4.406683 1.810820 H 3.919220 5.025791 1.012751 O 4.174508 3.593606 2.520292 C 0.151341 0.146942 0.232522 H 0.170232 0.558370 1.247095 C 1.290454 0.097616 0.286238 H 1.369077 0.689076 1.045504 C 1.867247 1.397568 0.940104 H 1.136032 1.754857 1.683785 C 2.101616 2.471774 0.088389 H 1.234609 2.726586 0.698361 O 2.022925 0.262099 0.884775 O 3.084014 1.113339 1.617353 C 3.225887 1.020484 0.667343 C 2.913415 0.706682 2.980628 C 3.940475 1.192225 1.984592 C 4.303298 2.462006 2.446157 C 4.294395 0.067712 2.743902 C 5.015589 2.607873 3.639706 H 4.035032 3.342353 1.865460 C 5.005038 0.20 8589 3.934857 H 4.008234 0.922325 2.403589 C 5.368790 1.481788 4.384640 H 5.293089 3.600755 3.984958 H 5.286582 0.681642 4.489987 H 5.927636 1.594290 5.310301 C 4.266031 0.428054 3.587206 C 4.524574 0.791560 4.220970 C 5.276248 1.398989 3.544851 C 5.767382 1.037735 4.809877 H 3.747932 1.552092 4.257012 C 6.519867 1.152859 4.124087 H 5.082031 2.347530 3.051417 C 6.767884 0.066855 4.760901 H 5.953143 1.989213 5.300901 H 7.296147 1.912600 4.083289 H 7.736555 0.257519 5.215189 H 3.860916 0.489204 0.049472 H 2.971774 1.998665 0.233678 H 2.272390 0.181945 3.048234 H 2.40 2210 1.517222 3.527204 C 5.523051 3.712081 2.650057 O 6.057494 3.175967 3.592271 C 6.287825 4.526916 1.621815 H 5.986570 5.580536 1.645364 H 6.127528 4.155918 0.604069 H 7.347887 4.457622 1. 866455 C 1.461725 1.608144 0.573317 C 2.267617 1.062020 1.616503 H 0.572601 2.148397 0.877236 H 1.945812 2.003497 0.310820 H 1.797279 1.056311 2.599742 C 3.765344 1.233620 1.662062 H 4.229437 0.893501 0.743296 H 4.179456 0.667046 2.497513 O 4.142742 2.633150 1.740316 C 4.425073 3.278530 2.899614 O 4.760743 4.440072 2.838375 C 4.324942 2.512482 4.206192 H 5.092524 1.732121 4.264430 H 3.352107 2.025572 4.328174 H 4.482197 3.219362 5.021218 TS20 E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93124402000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.86210693000 a.u Ru 1.422473 0.7080 36 0.320043 O 1.552248 3.665563 1.853153 O 0.073878 2.135846 1.246345 N 3.284500 0.071482 1.806371 N 3.103539 1.821183 0.699170 C 2.660686 0.523518 0.756161 C 4.043628 0.861954 2.644436 C 2 .737165 1.347820 2.295091 C 1.540802 1.075254 3.246568 C 0.889641 2.401584 3.678377 C 1.941131 3.265221 4.404427 C 3.126409 3.540803 3.455525 C 3.782316 2.199649 3.046090 C 2.604957 4.280715 2.204968 C 1.558148 3.405931 1.466638 C 2.256563 2.099260 1.037120 C 0.379487 3.132696 2.420219

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310 C 2.453778 2.948543 0.078115 C 1.320810 3.502448 0.721535 C 0.698093 4.617054 0.153779 C 0.781202 2.930615 2.014632 C 4.127443 2.097102 1.736247 C 3.004038 3.568075 1.058578 C 1.187943 5.214369 1.015255 C 2.342676 4.684866 1.591806 C 4.285008 3.107794 1.719075 C 0.507515 6.432212 1.595648 H 3.156608 2.388539 0.473241 H 5.027929 0.458981 2.897254 H 3.507303 1.069683 3.580440 H 0.801813 0.449262 2.728865 H 1.878891 0.515980 4.131002 H 0.049654 2.187402 4.350805 H 2.29 0838 2.753234 5.312604 H 1.492541 4.214651 4.726026 H 3.875186 4.158363 3.968902 H 4.649054 2.378643 2.395203 H 4.147510 1.679340 3.944490 H 3.435556 4.520472 1.527317 H 2.153100 5.236873 2. 505032 H 1.213852 3.944808 0.581413 H 0.386560 2.526400 1.920968 H 0.100487 4.078825 2.706191 H 0.181271 5.029247 0.644002 H 0.046475 3.542394 2.381750 H 1.550960 2.900673 2.796184 H 0.414448 1.905104 1.891508 H 3.902444 3.031586 2.256569 H 5.115709 2.198174 1.270126 H 2.759637 5.158208 2.478762 H 4.847731 3.972026 2.087751 H 4.099663 2.458615 2.583041 H 4.933407 2.561580 1.02869 7 H 0.582264 6.347112 1.527606 H 0.776714 6.581228 2.646286 H 0.793209 7.340873 1.049355 N 0.367395 3.295955 1.791847 O 0.576864 3.959507 2.227757 C 4.190442 2.769355 0.827085 H 5.009196 2. 165681 1.212476 C 4.592881 4.052047 0.152567 H 4.965977 4.773128 0.889913 H 5.409353 3.879275 0.558027 O 3.494250 4.723945 0.483906 C 0.095953 0.843969 1.000399 H 0.067859 1.689399 0.341083 C 1.486954 0.252110 0.925654 H 1.481824 0.745296 1.372221 C 2.539697 1.095208 1.714151 H 2.065291 1.376886 2.671213 C 2.933499 2.358401 0.997737 H 2.107999 2.965065 0.631680 O 1.787511 0.14714 2 0.467816 O 3.695304 0.308483 1.978413 C 2.845741 0.753104 0.792048 C 3.591306 0.522122 3.145100 C 2.966177 0.888666 2.293667 C 3.682216 1.969848 2.826205 C 2.418259 0.054234 3.171233 C 3.849646 2.105392 4.204009 H 4.107486 2.713419 2.155257 C 2.580582 0.083994 4.553014 H 1.858566 0.890972 2.767514 C 3.297307 1.161839 5.074724 H 4.405078 2.952273 4.598638 H 2.144386 0.654233 5.221804 H 3.422947 1.268903 6.148908 C 4.563333 1.668372 3.028884 C 4.107775 2.949178 2.689866 C 5.933390 1.460791 3.234822 C 5.013017 4.005385 2.561207 H 3.045029 3.126312 2.533196 C 6.837 620 2.514265 3.101814 H 6.290239 0.468285 3.501186 C 6.377308 3.790194 2.764922 H 4.647920 4.996385 2.305328 H 7.898386 2.342965 3.266333 H 7.080086 4.613703 2.667178 H 3.789804 0.387698 0.3 68972 H 2.648416 1.734487 0.336459 H 2.572700 0.917489 3.244439 H 3.801593 0.092004 4.034828 C 3.123454 4.441557 1.759577 O 2.094329 4.929995 2.175016 C 4.017883 3.557751 2.604459 H 5.013359 3.999094 2.727328 H 4.137511 2.566699 2.155095 H 3.554312 3.450985 3.585033 C 0.708261 0.765831 2.138566 C 2.480332 0.797412 1.834523 H 0.392862 0.169922 2.990945 H 1.443781 1.536952 2.337108 H 2.087489 1.427955 2.638503 C 3.889251 0.355784 2.067386 H 4.163250 0.496432 1.450609 H 4.540343 1.196083 1.781453 O 4.133222 0.051928 3.425106 C 4.428482 0.836450 4.427125 O 4.512431 0.4 08121 5.551174 C 4.662987 2.289535 4.059966 H 5.528173 2.392184 3.393994 H 3.801308 2.741721 3.557187 H 4.864775 2.833034 4.983238 TS21 E CB

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311 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.92915840000 a.u. M06/S DD/6 311++G(d,p) SCF energy in solution: 2838.86124466000 a.u Ru 1.601373 0.587970 0.628513 O 0.603734 2.832881 0.538017 O 0.798173 2.060270 2.033748 N 3.454142 0.037103 1.517158 N 2.791995 2.015793 0.824328 C 2.622619 0.662830 0.647500 C 4.110822 0.938608 2.468745 C 3.263463 1.399269 1.765593 C 2.187255 1.604535 2.864660 C 1.923306 3.107233 3.075867 C 3.233079 3.804735 3.492551 C 4.2901 96 3.607565 2.386223 C 4.567653 2.095406 2.212821 C 3.761302 4.210506 1.066147 C 2.450485 3.492601 0.641554 C 2.795451 2.001228 0.425752 C 1.403196 3.700522 1.754309 C 1.875531 3.082557 0.50 0587 C 0.728207 3.243768 1.312730 C 0.148271 4.298062 1.040160 C 0.413473 2.300890 2.451680 C 3.829201 2.311356 1.843572 C 2.182426 4.026182 0.498404 C 0.095934 5.208769 0.005221 C 1.268952 5.063247 0.736814 C 3.459502 3.995693 1.309552 C 0.866137 6.344372 0.256474 H 3.676230 1.988255 0.234355 H 5.180106 0.722984 2.544158 H 3.670870 0.835129 3.469544 H 1.260186 1.101245 2.561569 H 2.517050 1.142721 3.806560 H 1.166604 3.229139 3.861399 H 3.600299 3.396883 4.445542 H 3.054391 4.876696 3.651834 H 5.224485 4.108119 2.673275 H 5.350531 1.929652 1.459792 H 4.934445 1.68 0725 3.163879 H 4.518649 4.115713 0.275223 H 3.575829 5.285353 1.202303 H 2.088707 3.928382 0.295911 H 0.457554 3.230258 1.475500 H 1.205406 4.774751 1.877164 H 1.039105 4.408711 1.653651 H 0.400924 2.705822 3.057592 H 1.277758 2.142331 3.107511 H 0.092539 1.318025 2.088787 H 3.455269 3.044071 2.563181 H 4.719064 2.734996 1.361487 H 1.497500 5.783644 1.520139 H 3.789561 5.017264 1.525842 H 3.331612 3.493153 2.275351 H 4.273448 3.491740 0.781166 H 0.848121 6.652582 1.307443 H 0.610016 7.225749 0.346790 H 1.889776 6.058030 0.005546 N 0.145088 2.892569 1.698896 O 0.559581 3.678819 2.553816 C 4.434042 2.399159 0.690003 H 5.193269 1.794540 1.180992 C 4.933338 3.612412 0.051443 H 5.074204 4.460132 0.628980 H 5.906110 3.413339 0.514299 O 3.995769 4.096910 1.030888 C 0.161411 0.859544 1.019566 H 0.021813 1.679042 0.325732 C 1.470841 0.122193 0.833087 H 1.412544 0.876115 1.268680 C 2.658330 0.846104 1.550636 H 2.276880 1.187956 2.529758 C 3.15 0423 2.046481 0.783493 H 2.383746 2.647964 0.300659 O 1.648903 0.010515 0.575201 O 3.738073 0.054987 1.762472 C 2.660698 0.915372 1.002542 C 3.605585 0.873771 2.933667 C 2.474712 1.188680 2. 475929 C 2.376958 2.504006 2.944108 C 2.418902 0.136423 3.402143 C 2.237174 2.767542 4.309804 H 2.405503 3.325914 2.233195 C 2.268975 0.396428 4.764584 H 2.478962 0.890490 3.053695 C 2.181332 1.714142 5.223519 H 2.167416 3.795498 4.656327 H 2.223216 0.430367 5.469180 H 2.070027 1.916598 6.285696 C 4.621047 1.985828 2.869563 C 4.222071 3.292522 2.561698 C 5.977769 1.719260 3.095815 C 5.169628 4.316057 2.483372 H 3.169842 3.512080 2.391415 C 6.924168 2.740042 3.013792 H 6.290514 0.705883 3.337997 C 6.519987 4.042440 2.707092 H 4.849266 5.327642 2.248846 H 7.97403 1 2.522838 3.193611 H 7.255642 4.840502 2.647464 H 3.652322 0.485851 0.807819 H 2.578494 1.843283 0.427954 H 2.597399 1.302748 2.997609 H 3.758360 0.244192 3.825238 C 3.905049 3.517641 2.258 534 O 2.956147 3.799660 2.957677 C 5.012070 2.583939 2.704019 H 5.977922 3.101330 2.728764

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312 H 5.103737 1.727003 2.029250 H 4.771671 2.227450 3.705317 C 0.525897 0.933183 2.227477 C 2.627850 0.190257 2.113617 H 0.231977 0.318788 3.074054 H 1.134231 1.803334 2.450266 H 2.384095 0.795813 2.999108 C 3.838321 0.669004 2.296094 H 3.923577 1.430357 1.525502 H 4.722195 0.017870 2.221412 O 3.825655 1.385487 3.546458 C 4.330528 0.877185 4.712489 O 4.197849 1.528575 5.718238 C 5.052016 0.457192 4.667585 H 5.951690 0.399779 4.043592 H 4.418859 1.256907 4.269430 H 5.346137 0.707 478 5.686996 TS22 E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93226082000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.86150604000 a.u Ru 1.455369 0.688283 0.609791 O 0.512671 1.321237 3.387756 O 0.045529 2.143382 1.416460 N 3.609296 0.583503 1.317982 N 3.332107 1.523935 0.749688 C 2.868956 0.248633 0.536436 C 4.477370 0.120801 2.265859 C 3.116473 1.954010 1.526069 C 2.039872 1.972470 2.644941 C 1.439767 3.385003 2.779293 C 2.566084 4.377615 3.131022 C 3.634027 4.362343 2.016679 C 4.239845 2.942183 1.903897 C 2.972255 4.765121 0.680571 C 1.847282 3.760418 0.321316 C 2.487745 2.365405 0.182062 C 0.787224 3.778493 1.439185 C 2.623539 2.763724 0.552666 C 1.610754 3.106619 1.480620 C 0.938294 4.321934 1.327792 C 1.261815 2.207421 2.647263 C 4.495972 1.533817 1.669900 C 3.016734 3.672203 0.446129 C 1.266443 5.217229 0.300782 C 2.312164 4.880357 0.559088 C 4.170992 3.416843 1.389766 C 0.536476 6.533681 0.170055 H 3.319558 2.461113 0.532736 H 5.471841 0.33 1039 2.307852 H 4.047071 0.100183 3.276833 H 1.247572 1.252060 2.398309 H 2.480221 1.655304 3.601666 H 0.683387 3.379325 3.573941 H 3.020071 4.112689 4.096958 H 2.154956 5.390279 3.239033 H 4.436180 5.070442 2.263183 H 5.025371 2.918350 1.136196 H 4.706730 2.665270 2.861061 H 3.723887 4.793180 0.120969 H 2.559242 5.780253 0.766052 H 1.382605 4.045109 0.626819 H 0.027660 3.087701 1.196280 H 0.341878 4.779545 1.520056 H 0.151057 4.576008 2.034473 H 0.484168 2.668115 3.261045 H 2.132936 2.028202 3.290739 H 0.901010 1.224433 2.323313 H 4.385417 2.321811 2.418569 H 5.41 7133 1.726973 1.105315 H 2.605092 5.578893 1.340535 H 4.694535 4.354294 1.605377 H 3.837946 3.009290 2.351557 H 4.900375 2.718457 0.970138 H 0.536231 6.412059 0.354789 H 0.666912 6.968484 0. 826120 H 0.907096 7.264333 0.901127 N 0.695654 2.170065 2.487098 O 1.567607 3.041707 2.552924 C 4.070156 2.763782 0.644460 H 4.950642 2.301234 0.203936 C 4.343284 3.770594 1.726804 H 4.818175 4.664920 1.305479 H 5.040215 3.366225 2.470022 O 3.149307 4.260458 2.357677 C 0.120759 0.995959 0.665731 H 0.142909 1.600390 0.196286 C 1.514516 0.412301 0.618141 H 1.618065 0.354075 1.38630 1 C 2.615443 1.474797 0.943367 H 2.245570 2.050496 1.810620 C 2.861129 2.439166 0.185782 H 1.973753 2.909129 0.604660 O 1.666571 0.166052 0.674572 O 3.829763 0.826339 1.297694 C 2.643517 1.205588 0.760067 C 3.924549 0.482396 2.690200 C 2.633371 1.803841 2.148371 C 3.226894 3.056356 2.357916 C 2.080457 1.128745 3.243047 C 3.271978 3.619733 3.632884 H 3.651383 3.595815 1.513879 C 2.119226 1.695744 4.520284 H 1.611248 0.163375 3.086791 C 2.716395 2.941088 4.721045 H 3.733970 4.593231 3.775594 H 1.681123 1.160812 5.359699 H 2.746670 3.381424 5.714226

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313 C 5.106642 0.43 0734 2.888791 C 4.913773 1.800448 3.106995 C 6.411388 0.077481 2.837642 C 6.012334 2.646910 3.275542 H 3.903799 2.203472 3.145384 C 7.508322 0.767816 3.000838 H 6.564754 1.141413 2.670524 C 7.309354 2.133614 3.221750 H 5.851905 3.707644 3.449271 H 8.516427 0.362903 2.962071 H 8.163178 2.793141 3.354863 H 3.636326 0.800459 0.527176 H 2.421381 1.979755 0.011624 H 3.007515 0.015550 3.029697 H 4.038071 1.410328 3.273433 C 2.590682 3.633087 3.423833 O 1.500718 4.009044 3.799680 C 3.359493 2.518423 4.103188 H 4.318274 2.875908 4.495198 H 3.561264 1.694961 3.410520 H 2.75 3959 2.150750 4.931603 C 0.554981 1.249515 1.854170 C 2.257900 0.402758 2.248863 H 0.141947 0.910978 2.799012 H 1.311923 2.023880 1.893547 H 1.694650 0.812936 3.097230 C 3.600426 0.154823 2. 604646 H 4.016227 0.767510 1.807605 H 4.282604 0.694201 2.763602 O 3.560815 1.010869 3.763005 C 3.682017 0.552693 5.047161 O 3.573361 1.350508 5.944309 C 3.974643 0.920016 5.264733 H 4.947876 1.196624 4.842324 H 3.215367 1.563202 4.808277 H 3.994475 1.097148 6.340137 TS23 E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93112942000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.85598871000 a.u Ru 1.499222 0.947216 0.049553 O 0.417620 2.467810 2.337097 O 0.383477 2.803287 0.305652 N 3.306715 0.128023 2.038132 N 3.294320 1.691608 0.495797 C 2.759263 0.480395 0.842918 C 4.192523 1.142447 2.618525 C 2.696855 0.946002 2.828546 C 1.666583 0.357017 3.830803 C 0.953497 1.495573 4.585814 C 1.999803 2.331800 5.350773 C 3.017922 2.922655 4.353601 C 3.741743 1.772137 3.614864 C 2.27 0403 3.815579 3.340419 C 1.227100 2.972802 2.561410 C 1.971655 1.850115 1.828013 C 0.215210 2.380306 3.562748 C 2.799353 2.638542 0.471748 C 1.656310 3.404878 0.141517 C 1.154534 4.301750 1. 088552 C 1.013112 3.342312 1.228577 C 4.263765 2.192069 1.497935 C 3.504880 2.880152 1.665137 C 1.785757 4.495371 2.324791 C 2.966827 3.798001 2.579339 C 4.822027 2.217496 2.005875 C 1.221711 5.477907 3.324606 H 2.760924 2.331385 1.174396 H 5.172600 0.718023 2.857627 H 3.765635 1.548592 3.543300 H 0.939359 0.245912 3.273414 H 2.173699 0.306267 4.545525 H 0.235397 1.061714 5.29389 0 H 2.513846 1.707611 6.095484 H 1.504047 3.141918 5.901961 H 3.763164 3.518516 4.896433 H 4.492496 2.171671 2.919358 H 4.273506 1.140740 4.341836 H 2.981477 4.274656 2.639544 H 1.769850 4. 638757 3.868803 H 0.709508 3.600632 1.833419 H 0.538693 1.789124 3.027994 H 0.315830 3.191880 4.078459 H 0.255949 4.865817 0.850448 H 0.057207 3.871995 1.223778 H 1.652162 3.834190 1.975814 H 0.839472 2.320831 1.577512 H 3.976595 3.193369 1.831926 H 5.262644 2.260523 1.052728 H 3.496396 3.966731 3.515225 H 5.552051 2.975436 2.313094 H 4.723383 1.512468 2.839134 H 5.246810 1.673400 1.158903 H 1.554454 5.251288 4.342826 H 1.541535 6.502811 3.093881 H 0.126889 5.471409 3.308235 N 0.295155 3.217783 1.343814 O 0.795165 4.341509 1.283774 C 3.695732 2.082233 1.886782 H 4.542437 1.400809 1.940681 C 4.028550 3.546929 1.984223 H 4.185387 3.847755 3.026812 H 4.960739 3.764006 1.449939 O 2.972551 4.408916 1.525507 C 0.054217 0.216157 0.241672 H 0.167562 1.302 717 0.256370 C 1.404871 0.207627 0.277548 H 1.495258 1.283700 0.121712

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314 C 2.159701 0.113424 1.606805 H 1.503664 0.197025 2.429559 C 2.468377 1.584628 1.734964 H 1.614342 2.258462 1.676399 O 1.986629 0.493435 0.830669 O 3.334726 0.687018 1.626487 C 3.047749 0.217764 1.477318 C 3.585472 1.375097 2.865874 C 3.571234 0.609481 2.627409 C 4.946870 0.667703 2.880539 C 2.697884 1.303954 3.475929 C 5.443265 1.394783 3.965186 H 5.634126 0.138456 2.224167 C 3.192130 2.039015 4.553501 H 1.630878 1.274397 3.276870 C 4.566630 2.084581 4.803798 H 6.514082 1.427533 4.148745 H 2.504007 2.576527 5.201224 H 4.950203 2.655675 5.645197 C 4.636895 2.427217 2.623553 C 4.261510 3.694783 2.156526 C 5.993381 2.150986 2.830366 C 5.231200 4.665141 1.900871 H 3.208879 3.922177 2.001729 C 6.964548 3.121037 2.575735 H 6.289748 1.170362 3.197524 C 6.583425 4.380725 2.108993 H 4.929189 5.646154 1.543678 H 8.014599 2.895850 2.744532 H 7.336760 5.139652 1.913177 H 3.848 933 0.438385 0.763562 H 2.660008 1.183138 1.843395 H 2.655251 1.842619 3.208513 H 3.921520 0.655461 3.627326 C 2.782338 4.653459 0.200931 O 1.800652 5.287715 0.123781 C 3.798772 4.137882 0.7 93673 H 4.801533 4.527396 0.586014 H 3.842845 3.044613 0.768410 H 3.490891 4.457570 1.788951 C 1.451890 0.043079 2.169628 C 2.274821 1.169010 1.984260 H 0.513381 0.191383 2.686943 H 1.861560 0.959202 2.161299 H 1.858503 2.105314 2.348328 C 3.784741 1.096192 1.979025 H 4.134733 0.236120 1.414023 H 4.217606 1.998341 1.536646 O 4.310124 0.890980 3.311387 C 4.606640 1.912981 4.166533 O 4.995208 1.633147 5.274012 C 4.460595 3.340208 3.670472 H 5.158709 3.547588 2.850997 H 3.449018 3.551450 3.309555 H 4.689800 4.005080 4.503453 TS24 E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1647. 01318901000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1646.39932252000 a.u Ru 0.293964 0.334103 0.563566 O 1.255717 3.152235 1.184730 O 0.909784 1.298524 2.321428 N 0.975246 2.125669 0.725131 N 1.184403 2.255299 0.333938 C 0.093184 1.462283 0.236855 C 0.683041 3.537539 0.994714 C 2.286011 1.474790 0.594658 C 2.954950 1.853740 0.751621 C 4.270788 1.069859 0.926748 C 5.220240 1.403926 0.241247 C 4.551545 1.013109 1.575491 C 3.246824 1.827295 1.749017 C 4.241123 0.500256 1.564535 C 3.275012 0.835263 0.395663 C 1.972327 0.051239 0.640897 C 3.952328 0.438439 0.933881 C 2.5214 52 1.875922 0.021739 C 2.931304 2.006059 1.362120 C 4.239164 1.637979 1.693194 C 1.990670 2.521482 2.426607 C 0.862523 3.533011 1.006074 C 3.400548 1.399823 0.969334 C 5.136447 1.151668 0.73 6537 C 4.698537 1.045252 0.587384 C 2.975384 1.267033 2.413722 C 6.532905 0.726737 1.126703 H 1.632040 0.266618 1.664485 H 1.110023 3.861183 1.947283 H 1.086547 4.178324 0.198500 H 2.268038 1.627308 1.580416 H 3.147144 2.936180 0.780344 H 4.736414 1.357037 1.878190 H 5.466679 2.475313 0.239176 H 6.165954 0.858854 0.122706 H 5.226124 1.245934 2.409470 H 2.769914 1.593946 2.710267 H 3.480075 2.902609 1.749196 H 3.795829 0.802975 2.522251 H 5.175362 1.067783 1.453859 H 3.059935 1.909464 0.391234 H 3.304711 0.678248 1.783668 H 4.877554 1.015738 1.062549 H 4.564597 1.73 5401 2.726605 H 2.521630 2.673558 3.370784 H 1.531876 3.475258 2.139791 H 1.171932 1.815460 2.612984 H 1.296978 4.375518 0.461171 H 1.261673 3.538739 2.027759

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315 H 5.381556 0.667889 1.345406 H 3.036871 2.227465 2.943657 H 3.622955 0.562990 2.943978 H 1.945134 0.908294 2.502223 H 6.570444 0.349062 1.342482 H 7.250833 0.920821 0.322761 H 6.875435 1.251904 2.024268 N 1.363495 2.546220 2.266494 O 1.845305 3.017240 3.284933 C 0.815824 1.250645 0.536456 H 1.906116 1.155385 0.381898 C 0.429050 2.258815 1.585874 H 0.051388 1.749328 2.430891 H 0.295170 2.973893 1.183057 O 1.57 6486 2.911993 2.151932 C 2.109782 4.046558 1.601900 O 3.154416 4.453357 2.049719 C 1.339692 4.743494 0.498161 H 0.389351 5.137149 0.878098 H 1.093430 4.081587 0.337460 H 1.948410 5.575430 0.143152 12E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.94877846000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.88152090000 a.u Ru 1.689320 0.377046 0.726790 O 2.479812 0.236721 3.601828 O 0.558844 0.06610 4 2.538016 N 2.629102 2.380664 1.100623 N 2.992334 0.556173 2.249837 C 2.583943 1.027932 1.029789 C 2.890445 2.900392 2.446778 C 2.057556 3.192628 0.020711 C 0.573868 3.547816 0.311133 C 0. 017256 4.338317 0.873591 C 0.794830 5.631370 1.085657 C 2.266259 5.274123 1.381446 C 2.855946 4.502732 0.181063 C 2.336613 4.393740 2.644138 C 1.518958 3.090381 2.432591 C 2.147038 2.330060 1.253258 C 0.052630 3.461202 2.138081 C 3.411174 0.767552 2.617656 C 2.570962 1.572148 3.408277 C 3.030708 2.837084 3.801272 C 1.217296 1.106234 3.895226 C 3.395744 1.647269 3.167568 C 4.724377 1.189101 2.305391 C 4.300793 3.303501 3.462182 C 5.137634 2.454219 2.727051 C 5.687176 0.303512 1.545010 C 4.761657 4.684843 3.862325 H 3.210321 2.115233 1.475444 H 3.628115 3.706632 2.429213 H 1.965892 3.289654 2.892423 H 0.005186 2.629578 0.472580 H 0.508013 4.146331 1.230893 H 1.061929 4.583196 0.650087 H 0.731694 6.272368 0.194776 H 0.375157 6.206136 1.922070 H 2.849 287 6.191781 1.534358 H 3.914206 4.265224 0.355279 H 2.801758 5.128696 0.721420 H 3.380716 4.149092 2.882605 H 1.932691 4.942158 3.506127 H 1.587888 2.491025 3.341209 H 0.540235 2.551291 2.0 00991 H 0.371936 4.001420 2.995425 H 2.375453 3.467009 4.399786 H 0.443463 1.851846 3.678995 H 1.228145 0.967952 4.984121 H 0.917608 0.160239 3.440733 H 2.944017 1.503109 4.153219 H 4.485556 1.651542 3.290519 H 6.140801 2.788903 2.471790 H 6.111045 0.476637 2.191052 H 6.525760 0.890798 1.159219 H 5.208423 0.199973 0.700223 H 4.657489 5.388880 3.026708 H 5.817074 4.685661 4.156114 H 4.174743 5.077231 4.698851 N 1.241166 0.062590 3.661862 O 0.625043 0.108594 4.707720 C 3.654412 1.525368 2.254449 H 4.480978 1.767405 1.591126 C 3.969315 1.187218 3.682330 H 3.053723 1.1 48356 4.278815 H 4.636347 1.926919 4.137185 O 4.536697 0.139427 3.816569 C 0.264152 0.638393 0.259747 H 0.266576 0.476090 1.338004 C 1.162289 0.680292 0.280501 H 1.129788 0.847954 1.362957 C 2.005115 1.837115 0.361591 H 1.366271 2.739197 0.382906 C 2.408674 1.516136 1.775610 H 1.586515 1.253241 2.439891 O 1.738217 0.595123 0.005264 O 3.174463 2.132239 0.392468 C 2.816963 0.962745 0.882107 C 2.967291 2.980641 1.522489 C 3.484192 2.216485 0.371527 C 3.719128 3.298838 1.227594 C 3.936232 2.291163 0.953694 C 4.398458 4.432612 0.771987 H 3.373674 3.252848 2.258154 C 4.6 14967 3.420145 1.411836 H 3.758928 1.460423 1.628838

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316 C 4.847891 4.494727 0.547997 H 4.576076 5.263852 1.449921 H 4.978819 3.439440 2.435137 H 5.381748 5.373273 0.901540 C 4.307937 3.363767 2 .099655 C 4.622773 3.079078 3.431797 C 5.252883 4.026558 1.304035 C 5.857553 3.455953 3.966343 H 3.898786 2.559517 4.055169 C 6.487830 4.397654 1.832509 H 5.014708 4.245107 0.266231 C 6.792354 4.114701 3.167616 H 6.088274 3.229539 5.003779 H 7.212809 4.911408 1.206391 H 7.754150 4.406766 3.580778 H 3.541839 0.142078 0.925346 H 2.422832 1.118220 1.896796 H 2.356103 2.480005 2.2863 32 H 2.416422 3.879598 1.196862 C 5.874461 0.382717 3.805668 O 6.249358 1.529272 3.882170 C 6.830766 0.793650 3.717869 H 6.762399 1.428419 4.608976 H 6.628962 1.420798 2.843415 H 7.842441 0.393568 3.648092 C 1.206391 1.848793 0.147668 C 2.363284 1.463883 1.145212 H 0.587917 2.578455 0.679565 H 1.636736 2.296200 0.749846 H 2.078395 1.712214 2.167391 C 3.747070 1.994018 0.866910 H 3.990091 1.957413 0.191079 H 4.492279 1.418996 1.423875 O 3.827998 3.396548 1.210989 C 4.144940 3.824582 2.469107 O 4.067682 5.007575 2.700812 C 4.616968 2.804718 3.489993 H 5.563481 2.34 8801 3.174588 H 3.899446 1.993058 3.650920 H 4.780143 3.333274 4.429546 12E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.95253687000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.88478192000 a.u Ru 1.609255 0.617899 0.696627 O 0.534742 3.043669 0.592035 O 0.631790 1.961092 2.110062 N 3.767321 0.198807 1.182320 N 3.002111 1.835299 0.863829 C 2.809333 0.519328 0.537596 C 4.620173 0.592231 2.074643 C 3.612256 1.650247 1.306933 C 2.865872 1.999303 2.624154 C 2.622300 3.517669 2.710369 C 3.974932 4.257927 2.665486 C 4.703398 3.918626 1.349041 C 4.967819 2.396830 1.287062 C 3.824674 4.35 1272 0.156745 C 2.465873 3.598251 0.198824 C 2.776860 2.098884 0.103089 C 1.744647 3.940770 1.518103 C 2.063839 2.929014 0.779417 C 0.989966 2.960502 1.701347 C 0.095381 4.032292 1.655098 C 0.786301 1.874173 2.734336 C 4.153369 2.026056 1.779214 C 2.294735 4.013417 0.087635 C 0.253273 5.084084 0.743023 C 1.362576 5.061839 0.101958 C 3.512267 4.136602 0.978721 C 0.729944 6.231470 0.724593 H 3.377118 1.922885 0.826605 H 5.678587 0.440055 1.841460 H 4.460428 0.308260 3.121667 H 1.910371 1.460687 2.647330 H 3.456328 1.662863 3.487654 H 2.106038 3.743286 3.652198 H 4.595572 3.972327 3.526887 H 3.813255 5.341818 2.734413 H 5.665261 4.446386 1.311141 H 5.518019 2.135594 0.372682 H 5.590003 2.093466 2.141683 H 4.341622 4.149156 0.791737 H 3.646924 5.434559 0.198078 H 1.852454 3.907204 0.649280 H 0.773603 3.437085 1.553929 H 1.549017 5.020800 1.556711 H 0.741206 4.046265 2.349445 H 0.013845 2.177516 3.445678 H 1.703773 1.669604 3.300087 H 0.463 493 0.929665 2.282994 H 3.831907 2.564575 2.675705 H 4.929328 2.624450 1.289255 H 1.527345 5.890045 0.788869 H 3.946171 5.138222 0.879431 H 3.258298 3.999987 2.035969 H 4.291189 3.413387 0.7 25990 H 0.766491 6.713561 0.258129 H 0.450919 7.001075 1.456848 H 1.736349 5.887609 0.983688 N 0.267912 2.858510 1.793365 O 0.817382 3.462599 2.718342 C 4.231536 2.403650 0.131189 H 5.013179 1.889514 0.685892 C 4.689038 3.534837 0.751356 H 4.839204 4.451270 0.168790 H 5.650097 3.298949 1.221563 O 3.715224 3.903119 1.745722

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317 C 0.004927 0.601826 0.612222 H 0.073159 1.415740 0.102529 C 1.409418 0.012595 0.563332 H 1.444887 0.935182 1.101784 C 2.518791 0.912480 1.199665 H 2.103244 1.371485 2.113943 C 2.961834 2.021560 0.280569 H 2.169633 2.532799 0.261199 O 1.643952 0.2 24392 0.822492 O 3.647153 0.121289 1.560119 C 2.660213 1.184470 1.124603 C 3.540794 0.509834 2.842932 C 2.591150 1.526067 2.595177 C 2.824182 2.838773 3.022445 C 2.332933 0.539370 3.557417 C 2.811261 3.160494 4.381704 H 3.011387 3.615672 2.284711 C 2.310610 0.860991 4.915527 H 2.138392 0.479659 3.238960 C 2.553691 2.172211 5.333232 H 2.993298 4.185519 4.694744 H 2.102936 0.084533 5.647949 H 2.537807 2.421735 6.391135 C 4.665557 1.502549 2.991703 C 4.420069 2.875627 2.868109 C 5.973051 1.060255 3.231762 C 5.468743 3.790963 2.985746 H 3.406489 3.228002 2.688029 C 7.0 21030 1.973202 3.345357 H 6.167124 0.005472 3.331594 C 6.769318 3.342511 3.222498 H 5.266792 4.854866 2.893804 H 8.031337 1.619323 3.534541 H 7.584091 4.056067 3.315738 H 3.646936 0.771300 0 .871854 H 2.511404 2.085002 0.517272 H 2.577920 1.027172 2.944346 H 3.589239 0.264628 3.626086 C 3.603953 3.209280 2.910872 O 2.629099 3.404934 3.604052 C 4.720551 2.263303 3.301995 H 5.669952 2.800264 3.410472 H 4.857686 1.477814 2.552467 H 4.456567 1.803436 4.253776 C 0.597747 1.028633 2.010909 C 1.949792 0.308106 2.422985 H 0.124922 0.783322 2.792148 H 0.788908 2.103297 1.9764 79 H 1.764462 0.397733 3.237721 C 3.153874 1.176246 2.691652 H 3.434300 1.747477 1.811917 H 4.006133 0.552581 2.981480 O 2.892768 2.178884 3.704359 C 3.075174 1.964811 5.039090 O 2.753364 2.839079 5.806562 C 3.701733 0.655905 5.485289 H 4.729052 0.563959 5.113806 H 3.139176 0.213748 5.130977 H 3.720104 0.652422 6.575310 12E B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.94387140000 a.u. M 06/SDD/6 311++G(d,p) SCF energy in solution: 2838.87711873000 a.u Ru 1.627636 0.454887 0.791811 O 0.007399 1.742659 3.014420 O 0.451311 0.387658 2.634188 N 2.677600 2.517173 0.906455 N 3.071359 0.723438 2.0 96813 C 2.609043 1.160274 0.881405 C 3.003787 3.072566 2.223583 C 2.072565 3.312535 0.166715 C 0.634650 3.764172 0.209706 C 0.001117 4.527937 0.969575 C 0.861923 5.759077 1.312003 C 2.285105 5.302330 1.694444 C 2.921433 4.563575 0.495695 C 2.210313 4.355438 2.910657 C 1.341642 3.116032 2.567695 C 2.016960 2.390542 1.394072 C 0.075367 3.587203 2.187086 C 3.488260 0.594378 2.489768 C 2.661557 1.369466 3.323980 C 3.107401 2.639639 3.714118 C 1.351046 0.856380 3.876792 C 3.533563 1.837552 2.955888 C 4.789760 1.037210 2.159223 C 4.355428 3.137191 3.337038 C 5.189729 2.3 07833 2.578201 C 5.771061 0.163183 1.406566 C 4.795990 4.527770 3.727146 H 3.055773 2.115538 1.685303 H 3.743833 3.873594 2.149593 H 2.102593 3.479699 2.699855 H 0.024337 2.887165 0.461775 H 0.669199 4.409203 1.098872 H 1.010712 4.844633 0.681428 H 0.902100 6.447783 0.456096 H 0.410721 6.313056 2.145893 H 2.902631 6.176074 1.940640 H 3.950349 4.257553 0.729552 H 2.967475 5.239487 0.370469 H 3.220407 4.041797 3.210408 H 1.773467 4.884125 3.768893 H 1.287007 2.448670 3.430115 H 0.705548 2.720389 1.965694 H 0.530806 4.109141 3.039799 H 2.460358 3.248764 4.342246 H 0.563488 1.613103 3.792395

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318 H 1.454267 0.626813 4.945727 H 1.012518 0.051552 3.374504 H 3.133015 1.729689 3.967889 H 4.628407 1.833059 3.020407 H 6.181063 2.661523 2.303115 H 6.311717 0.501309 2.093824 H 6.522946 0.775425 0.899187 H 5.284588 0.467307 0.657437 H 4.641469 5.231591 2.899222 H 5.861607 4.554585 3.979902 H 4.231714 4.901441 4.587509 N 0.123826 0.542165 3.350669 O 0.774 409 0.182037 4.330383 C 3.466900 1.850648 2.455015 H 4.286352 2.153488 1.807866 C 3.767310 1.567101 3.897562 H 2.841258 1.467307 4.470431 H 4.360362 2.366403 4.353901 O 4.433270 0.291869 4.0 76959 C 0.360364 0.680076 0.280670 H 0.451422 0.528230 1.356047 C 1.102025 0.771475 0.130796 H 1.167731 0.919567 1.209098 C 1.856461 1.988249 0.511992 H 1.169430 2.853317 0.497731 C 2.241496 1.723808 1.941580 H 1.425032 1.399889 2.586188 O 1.694664 0.471370 0.239027 O 3.017271 2.305853 0.244180 C 2.831874 0.847333 0.559370 C 2.771356 3.213459 1.333388 C 3.490761 2.062272 0.045308 C 3.707783 3.216428 0.716093 C 3.947054 2.030404 1.370873 C 4.372201 4.317131 0.166394 H 3.365404 3.250732 1.747981 C 4.612388 3.124726 1.922279 H 3.785372 1.142212 1.972958 C 4.826067 4.2 72670 1.152801 H 4.538602 5.204636 0.772138 H 4.982493 3.059451 2.941501 H 5.350464 5.124858 1.577981 C 3.941520 3.177466 2.282126 C 3.826816 2.530379 3.519149 C 5.159794 3.775193 1.933480 C 4.915362 2.485515 4.393341 H 2.884308 2.065613 3.800982 C 6.248065 3.727291 2.803946 H 5.251931 4.280519 0.974556 C 6.126325 3.081830 4.037744 H 4.814390 1.984228 5.352195 H 7.188217 4.196008 2.524365 H 6.972323 3.047303 4.719437 H 3.537102 0.009977 0.598397 H 2.500832 1.054456 1.587543 H 1.857192 2.932106 1.868390 H 2.627812 4.224564 0.919247 C 5.784919 0.153731 4.117430 O 6.244473 0.958802 4.228873 C 6.649306 1.399891 4.041212 H 6.492115 2.046129 4.912522 H 6.437471 1.990441 3.143823 H 7.691318 1.079990 4.023601 C 1.346467 1.796539 0.241680 C 2.432379 1.300540 1.292796 H 0.752930 2.530930 0.789055 H 1.865493 2.246622 0.605630 H 2.098925 1.548141 2.301342 C 3.851204 1.751159 1.055331 H 4.169702 1.550040 0.038223 H 4.534755 1.247874 1.747085 O 3.97 1189 3.188932 1.180797 C 4.222272 3.817216 2.364138 O 4.242388 5.024434 2.375825 C 4.498803 2.971606 3.595049 H 5.414838 2.381877 3.472070 H 3.680107 2.278391 3.812261 H 4.627595 3.649300 4. 439169 13E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 2839.93709316000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 2838.86738156000 a.u Ru 1.529805 0.510009 0.366942 O 1.909367 3.231586 2.180323 O 0.307648 1.977764 1.316168 N 3.028997 0.203861 2.019194 N 2.763098 2.105895 0.960541 C 2.488465 0.776106 0.914118 C 3.505578 1.188722 2.997232 C 2.583390 1.159181 2.346245 C 1.214071 1.109880 3.074296 C 0.689 217 2.536931 3.315686 C 1.706027 3.306534 4.182893 C 3.066894 3.357720 3.457635 C 3.588440 1.917148 3.237683 C 2.883876 4.069251 2.100302 C 1.874485 3.286780 1.219255 C 2.454083 1.873424 0.9 79371 C 0.518830 3.236110 1.952198 C 2.223996 3.151383 0.134274 C 1.024940 3.771718 0.550614 C 0.500868 4.808728 0.226425 C 0.306765 3.338921 1.810296 C 3.599508 2.454832 2.131901 C 2.919584 3.603001 0.999815 C 1.153010 5.257981 1.382486 C 2.357472 4.650299 1.743919 C 4.237117 3.004588 1.433249

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319 C 0.582548 6.400943 2.189920 H 3.479603 2.024153 0.618635 H 4.468528 0.896970 3.423985 H 2.783887 1.302046 3.818249 H 0.493006 0.544548 2.468106 H 1.313774 0.577679 4.031472 H 0.277297 2.482594 3.831214 H 1.813848 2.819253 5.162637 H 1.345469 4.326589 4.372120 H 3.792799 3.9 07575 4.071122 H 4.573907 1.935120 2.752225 H 3.710994 1.417286 4.210452 H 3.848248 4.154149 1.580701 H 2.522368 5.093749 2.268081 H 1.769181 3.805979 0.263131 H 0.222076 2.701646 1.344714 H 0.133427 4.254931 2.097723 H 0.434898 5.270705 0.081198 H 0.612978 3.914384 1.940301 H 0.925338 3.497412 2.703397 H 0.048123 2.273647 1.788788 H 3.217581 3.350148 2.627927 H 4.628601 2.657046 1.807235 H 2.887518 5.002826 2.626495 H 4.814706 3.730540 2.013933 H 4.105803 2.120754 2.067109 H 4.849408 2.694992 0.580683 H 0.506750 6.323574 2.275143 H 1.004304 6.429469 3.199765 H 0.799339 7.366598 1.714310 N 0.698471 3.043990 1.984340 O 0.187877 3.796940 2.393115 C 4.642572 2.374197 1.055881 H 5.392873 1.630954 1.316464 C 5.175778 3.672236 0.514313 H 5.708534 4.223011 1.298831 H 5.898783 3.492812 0.289982 O 4.139767 4.568298 0.084024 C 0.377009 1.029304 1.210360 H 0.274108 1.881426 0.545636 C 1.639064 0.222010 1.041570 H 1.473563 0.789050 1.425989 C 2.82 4623 0.832254 1.857376 H 2.419112 1.069153 2.856891 C 3.352185 2.106910 1.257631 H 2.599168 2.854581 1.017664 O 1.889620 0.162203 0.364492 O 3.874787 0.116837 1.990989 C 2.789265 0.868702 0. 774441 C 3.695122 1.040588 3.075792 C 2.897066 0.886469 2.281926 C 3.357365 2.044312 2.923664 C 2.596518 0.240184 3.056873 C 3.519633 2.074986 4.309107 H 3.588512 2.928586 2.333433 C 2.752065 0.208151 4.445286 H 2.231192 1.136084 2.566221 C 3.215796 0.947233 5.076445 H 3.876990 2.981851 4.790058 H 2.509628 1.089453 5.034348 H 3.337247 0.971308 6.156139 C 4.559065 2.253790 2.84496 0 C 3.976346 3.478973 2.497288 C 5.952907 2.165523 2.958019 C 4.778623 4.600029 2.269513 H 2.894039 3.557743 2.412077 C 6.754059 3.282648 2.724639 H 6.408987 1.216242 3.229821 C 6.166673 4. 503643 2.380692 H 4.316037 5.547847 2.007626 H 7.834347 3.204304 2.816470 H 6.790020 5.376601 2.204897 H 3.776077 0.703031 0.326065 H 2.429530 1.841003 0.406396 H 2.645184 1.350505 3.148156 H 3.960639 0.532847 4.016650 C 3.628937 4.525668 1.172904 O 2.635272 5.178673 1.409006 C 4.337027 3.691207 2.221198 H 5.370117 4.025916 2.367376 H 4.359524 2.633242 1.940095 H 3.793830 3.80138 0 3.159861 C 0.479669 0.901731 2.253628 C 2.932160 0.538082 1.541605 H 0.342920 0.135217 3.011882 H 1.254061 1.640406 2.426118 H 2.684578 0.623794 2.610345 C 4.414703 0.617959 1.313144 H 4.742004 0.007141 0.479696 H 4.670845 1.656520 1.061894 O 5.160165 0.159842 2.452833 C 5.466944 0.976189 3.510883 O 5.974877 0.470428 4.481453 C 5.182557 2.459863 3.384629 H 5.760723 2.901479 2.563789 H 4.125371 2.671729 3.193181 H 5.483540 2.933163 4.319589 14E CB B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1647.01384718000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1646.40176884000 a.u Ru 0.336889 0.300 383 0.696428 O 1.353532 3.300851 1.029338 O 1.097087 1.460982 2.228517 N 0.946744 2.109602 0.752558 N 1.211582 2.218117 0.370015 C 0.103448 1.460758 0.216772 C 0.621949 3.483441 1.154330

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320 C 2.268969 1.483463 0.619677 C 2.966091 1.939311 0.687958 C 4.299812 1.186408 0.865173 C 5.211769 1.478402 0.343708 C 4.515438 1.010473 1.638377 C 3.193172 1.793249 1.815850 C 4.228192 0.504088 1.545608 C 3.301253 0.795831 0.334539 C 1.976971 0.045827 0.574391 C 4.011938 0.325460 0.953272 C 2.545215 1.834179 0.004486 C 3.014204 2.178769 1.280173 C 4.314193 1.813721 1.632188 C 2.129 531 2.906402 2.265697 C 0.923915 3.453407 1.131902 C 3.360527 1.144582 0.918443 C 5.154381 1.124440 0.747034 C 4.658232 0.799321 0.516084 C 2.890690 0.746919 2.300012 C 6.566674 0.764687 1.1 45828 H 1.608035 0.322062 1.573254 H 1.024289 3.716868 2.143436 H 1.031349 4.206737 0.436180 H 2.303559 1.741342 1.544449 H 3.137805 3.025346 0.660958 H 4.785904 1.528621 1.787814 H 5.438749 2.552598 0.401365 H 6.169933 0.955866 0.223843 H 5.163701 1.212494 2.500856 H 2.695523 1.503562 2.750987 H 3.406935 2.870939 1.875934 H 3.759965 0.858046 2.474421 H 5.173068 1.053891 1.435619 H 3.103216 1.871403 0.277836 H 3.396970 0.543402 1.832698 H 4.953226 0.877282 1.077531 H 4.681040 2.069426 2.624020 H 2.678374 3.131215 3.184847 H 1.755138 3.854339 1.859926 H 1.253201 2.3 04741 2.535623 H 1.360971 4.324752 0.636510 H 1.349999 3.383241 2.140889 H 5.291254 0.253969 1.213147 H 3.527591 1.195356 3.072486 H 2.942467 0.340426 2.429513 H 1.859871 1.053004 2.491543 H 6.625187 0.486212 2.203555 H 6.949207 0.071831 0.552675 H 7.247838 1.612992 0.995609 N 1.581076 2.694920 2.088818 O 2.203838 3.153659 3.035667 C 0.796972 1.314223 0.270792 H 1.821055 1.408045 0.143041 C 0.541704 2.170000 1.479762 H 0.125593 1.572818 2.297515 H 0.196023 2.938592 1.224381 O 1.754495 2.733514 2.007087 C 2.271809 3.912330 1.536082 O 3.373870 4.232631 1.909290 C 1.413313 4.757510 0.616820 H 0.523455 5.119820 1.145460 H 1.057090 4.211192 0.261775 H 2.008915 5.614441 0.301175 Allyl Acetate B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 345.7690758600 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 345.6577357870 a.u C 3.189837 0.017443 0.368732 C 2.108807 0.248792 0.362285 H 4.134687 0.489436 0.195084 H 3.174210 0.754937 1.168671 H 2.141581 0.998641 1.150992 C 0.794085 0.451151 0.195710 H 0.570145 1.056851 1.084914 H 0.817797 1.116388 0.676087 O 0.220302 0.559703 0.035433 C 1.541695 0.237446 0.053089 O 2.346243 1.128148 0.174959 C 1.923165 1.230216 0.00614 9 H 1.639047 1.677450 0.965452 H 1.430214 1.806930 0.784202 H 3.004011 1.302895 0.115038 Hoveyda Ligand (CH 2 =CHR2) B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 502.80530553800 a.u. M06/SDD/6 311++G(d,p ) SCF energy in solution: 502.56274361400 a.u O 1.064396 0.477637 0.143742 C 1.250682 1.935382 0.027790 C 1.290056 0.464152 0.062418 C 2.494066 0.254500 0.060947 C 3.301534 0.919122 0.758452 C 2.363346 0.139428 0.188458 C 0.078513 0.272080 0.120226 C 2.522924 1.646813 0.094372 C 2.783720 0.605638 1.206006 C 0.103106 1.671725 0.154656 C 1.321874 2.352239 0.140173 H 0.312806 2.379202 0.3496 59 H 3.428708 0.299004 0.053653 H 3.322323 1.800242 0.107979 H 4.319587 0.522932 0.837922 H 2.970102 1.232346 1.753168 H 2.329144 0.991477 0.880352 H 3.472843 2.173411 0.094338 H 2.071614 1 .323926 1.622639 H 3.769727 1.082635 1.168300 H 2.839674 0.251747 1.885514 H 0.818551 2.240314 0.187263

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321 H 1.323123 3.438678 0.169132 C 2.238958 2.746996 0.370925 H 2.119332 3.826001 0.342212 H 3.189596 2.378498 0.748110 Norbornene B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 351.35291163200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 351.16691991000 a.u C 0.638802 0.790678 0.634559 C 0.850987 1.126412 0.251 198 C 0.850794 1.126564 0.250916 C 0.638875 0.790631 0.634474 H 0.790197 1.129993 1.667938 H 0.790274 1.130105 1.667790 C 1.593464 0.000242 1.007236 H 2.672176 0.000281 0.821457 H 1.405766 0.000384 2.088391 C 1.072273 0.670550 1.184879 C 1.072148 0.670390 1.185052 H 1.139875 2.156960 0.477114 H 1.139500 2.157223 0.476580 H 1.117128 1.326899 2.048464 H 1.116807 1.326544 2.048795 C 1.686357 1.489638 0.234934 H 2.704877 1.237631 0.082221 H 1.579916 2.578994 0.157588 H 1.589452 1.220186 1.291560 C 1.686115 1.489830 0.234860 H 1.579660 2.579205 0.157736 H 2.704715 1.237994 0.082187 H 1.589263 1.220260 1.291486 Norbornene* B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 916.03203380000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 915.75811831100 a.u C 3.447291 0.358123 1.540282 C 2.923046 0.876285 0.732161 C 3.812639 0.450233 0.875194 C 4.061881 1.270010 0.435502 H 2.618035 0.859887 2.048215 H 3.542824 2.231506 0.385158 C 2.434886 0.180873 0.571810 H 2.120414 0.888102 1.346267 C 4.134638 1.590572 0.162433 C 4.662721 0.804051 0.788354 H 2.201231 1.495370 1.269044 H 3.884638 1.029273 1.798304 H 4.528098 2.532300 0.532063 H 5.576192 0.970928 1.350105 H 5.127 644 1.464529 0.584569 H 4.174073 0.053545 2.298349 O 1.449476 0.834883 0.399551 C 0.134001 0.498161 0.294168 C 0.360294 0.813348 0.282027 C 0.759616 1.577476 0.201128 C 1.734159 1.031443 0.1 80765 H 0.309176 1.662272 0.348437 C 2.123578 1.348896 0.097685 H 0.357841 2.585396 0.218983 C 2.622344 0.039863 0.088635 H 2.114120 2.047945 0.178395 H 2.808758 2.188034 0.034145 C 4.092304 0.204986 0.082285 F 4.451007 0.268468 1.388917 F 4.835746 0.780544 0.472569 F 4.481053 1.372247 0.481206 Cyclobutene B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 847.1113359600 a.u. M06/SDD/6 311++G(d,p) SCF energy in so lution: 846.72764122500 a.u C 0.354896 3.781204 0.949404 H 0.957732 4.388162 1.619241 C 0.748267 2.896085 0.212145 H 1.219171 3.416376 1.063986 C 0.808357 2.665983 0.402448 H 1.223483 3.061193 1. 345482 C 0.962838 3.593478 0.797652 H 1.833283 4.009533 1.297902 O 1.518665 1.785123 0.163678 O 1.159073 1.309430 0.255153 C 1.866703 0.934738 0.922357 C 2.556637 1.074876 0.266375 C 2.638040 0.259779 0.408688 C 3.464138 0.980423 1.279494 C 2.508813 0.691368 0.916039 C 4.142446 2.117074 0.839746 H 3.579572 0.648890 2.309791 C 3.193352 1.824919 1.358692 H 1.880908 0.123962 1.594531 C 4.009200 2.543285 0.483403 H 4.781029 2.664839 1.528092 H 3.088859 2.146164 2.392078 H 4.541293 3.425498 0.829650 C 2.835167 0.404950 0.120426 C 1.883806 1.273140 0.424995 C 4.08156 4 0.914293 0.504519 C 2.177651 2.629109 0.582089 H 0.913305 0.883094 0.712056 C 4.377906 2.267023 0.339644 H 4.825192 0.248521 0.939005 C 3.424202 3.130059 0.204552 H 1.427131 3.295015 1.000 147 H 5.349387 2.648185 0.643813 H 3.650395 4.185907 0.328093 H 3.001711 1.453112 1.202890 H 3.035727 1.630288 0.558314 H 2.473542 1.490907 1.657506 H 0.954399 0.598439 1.435554

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322 E R1 CH=CHR2 B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 769.9875773170 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 769.6807551870 a.u C 0.312677 0.212774 0.194529 H 0.201432 0.831268 0.088445 C 0.921119 1.008797 0.138283 C 2. 177717 0.350685 0.112901 C 0.910368 2.410645 0.088024 C 3.361994 1.094748 0.046865 C 2.086730 3.153302 0.029646 H 0.046330 2.924638 0.072031 C 3.312240 2.488953 0.010562 H 4.325424 0.599554 0.026204 H 2.045773 4.237550 0.014374 H 4.240720 3.051252 0.041763 O 2.128847 1.013407 0.185195 C 3.319378 1.813229 0.051843 H 4.116999 1.364126 0.658124 C 3.752116 1.901226 1.411688 H 4.66063 3 2.506962 1.503900 H 2.962153 2.369932 2.008667 H 3.956169 0.912329 1.832277 C 2.963158 3.173440 0.641435 H 3.828529 3.843617 0.602916 H 2.647671 3.070475 1.684106 H 2.144690 3.632460 0.076 185 C 1.524728 0.644872 0.573053 H 1.687091 1.670461 0.898528 C 2.730470 0.238537 0.609578 H 3.117970 0.324568 1.634474 H 2.483034 1.244248 0.249536 O 3.745818 0.361857 0.227135 C 4.982443 0.191425 0.355966 O 5.799285 0.368665 1.046423 C 5.262680 1.491943 0.375096 H 4.566090 2.281000 0.070823 H 5.166300 1.369652 1.459728 H 6.281392 1.799594 0.138703 Z product ( CH 2 =CHR3) B3LYP/SDD/6 31G( d) SCF energy in gas p hase: 697.14253205100 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 696.84823194900 a.u C 1.332408 0.759944 1.529280 H 1.655816 0.728677 2.568305 C 2.503923 1.156094 0.493401 C 2.957180 0.28 2109 0.882670 C 0.618339 0.432244 0.098962 C 0.960952 1.033633 0.597192 H 2.864912 1.877264 1.239831 H 0.733483 1.034518 1.672453 C 1.981935 1.186711 0.106839 H 2.339448 1.320351 0.921605 H 1.899589 2.188228 0.542053 C 4.426820 0.560632 0.720478 C 0.050642 0.492536 1.248071 H 2.729647 0.386793 1.957130 H 0.047419 0.880343 0.843330 H 5.081675 0.134505 1.250276 C 0.139264 2.161696 0.030453 H 0.393215 3.123832 0.430966 H 0.933231 1.991366 0.112565 H 0.308570 2.251977 1.108004 C 3.022619 1.607120 0.879561 H 4.117564 1.613336 0.897658 H 2.678497 2.619547 1.114711 H 2.69 0400 0.948548 1.690586 C 2.418130 1.060541 0.540103 H 3.037709 1.891383 0.899027 O 3.235296 0.129959 0.412227 C 4.385358 0.130291 0.317680 O 5.014241 1.156902 0.405616 C 4.815254 1.167633 0. 977124 H 5.043466 1.934833 0.228400 H 4.033884 1.569542 1.631093 H 5.711393 0.966724 1.564449 H 0.601496 0.276309 2.095858 H 2.014142 1.333324 0.439764 C 4.986039 1.554585 0.027825 H 6.065260 1.674332 0.017326 H 4.397926 2.290337 0.514560 E product ( CH 2 =CHR4) B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 697.14704072200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 696.85227826900 a.u C 1.653468 1.620781 0.719400 H 1.539654 2.261487 1.595806 C 3.012597 1.690801 0.075051 H 3.175403 2.685584 0.357898 H 3.803503 1.543315 0.821404 O 3.172505 0.788811 1.025890 C 3.578849 0.503036 0.852650 O 3.599786 1.2 29053 1.816175 C 4.005009 0.945956 0.534724 H 4.910417 0.417867 0.855682 H 3.221987 0.756674 1.275478 H 4.218684 2.014056 0.491070 C 2.285540 1.025628 0.450264 C 3.012882 0.297963 0.068629 C 0.745832 0.882128 0.919878 C 1.234162 0.513588 1.470287 H 2.991483 1.697591 0.956381 H 1.799853 0.284295 2.384712 C 1.848859 1.304816 0.101033 H 1.455650 1.245532 1.124187 H 2.174682 2.339883 0.043801 C 3.936903 0.235317 1.113610 C 0.621099 0.891221 0.288596

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323 H 3.604274 0.598310 0.945609 H 0.724908 1.589189 1.758143 H 3.469038 0.034303 2.078593 H 0.753613 0.279300 0.603522 C 0.133758 1.499284 1.868377 H 0.567746 2.419596 2.277962 H 0.514718 1.067235 2.639833 H 0.503750 1.779855 1.023800 C 1.701718 1.789534 0.747733 H 2.499359 2.123432 1.419833 H 1.161093 2.681784 0.415428 H 1.003572 1.185360 1.338950 C 5.257848 0.417430 1.065104 H 5.771767 0.628832 0.129057 H 5.877744 0.363369 1.956153 Z product* ( CH 2 =CHR6) B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1261.8220834200 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1261.4390721500 a.u C 3.394702 0.102137 1.505852 H 3.863509 0.347315 2.457248 C 3.150903 1.282680 0.615671 H 2.391672 1.935858 1.067460 H 2.786838 0.983317 0.371651 O 4.398722 1.997754 0.502656 C 4.480608 3.190186 0.150265 O 5.551758 3.742622 0.212733 C 2.855481 3.145325 0.378628 C 2.420663 1.718333 0.007446 C 0.433240 3.104054 0.657165 C 1.741675 3.608260 1.327645 H 3.851117 3.164652 0.833351 H 1.863254 3.123245 2.304188 C 0.866290 1.791147 0.084567 H 0.527221 1.795265 1.127138 C 3.071102 1.170256 1.249395 C 0.128340 4.129286 0.295541 H 2.633610 1.063880 0.846241 H 0.329068 2.860683 1.404654 H 3.276915 1.906511 2.027955 H 0.539219 4.458295 1.094665 H 1.732082 4.689490 1.497163 H 2.897069 3.787324 0.512483 O 0.382 150 0.596818 0.549056 C 0.897143 0.171897 0.341732 C 1.869538 0.873098 0.382053 C 1.218935 1.065613 0.923608 C 3.144888 0.324934 0.528727 H 1.656175 1.844494 0.811759 C 2.490622 1.597634 0.7 75252 H 0.454818 1.587694 1.490639 C 3.464513 0.905336 0.043304 H 3.898516 0.872214 1.085194 H 2.734870 2.551004 1.233073 C 4.819030 1.518542 0.158218 F 4.820534 2.427460 1.164374 F 5.242162 2.173178 0.948848 F 5.756924 0.594595 0.466214 C 3.213042 3.757726 0.762587 H 2.758613 3.058352 1.472987 H 2.464168 3.977620 0.006794 H 3.473122 4.681035 1.280430 C 1.349200 4.662508 0.218672 H 1.691408 5.412392 0.926749 H 2.050996 4.373838 0.561405 E product* ( CH 2 =CHR7) B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1261.82473135000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1261.44091856000 a.u C 2.062062 1 .273569 1.391764 H 1.967844 0.929005 2.422502 C 1.901266 2.759067 1.210949 H 0.871142 3.054073 1.445054 H 2.550410 3.308924 1.903554 O 2.104757 3.191607 0.138527 C 3.346290 3.490568 0.624694 O 3.452219 3.744778 1.799117 C 4.515235 3.508378 0.342633 H 4.399960 4.305478 1.086219 H 4.609195 2.558181 0.877771 H 5.420881 3.694884 0.234722 C 3.630157 1.716969 0.067807 C 2.369566 1.0913 58 0.586833 C 1.756466 3.353969 0.068416 C 3.233765 3.159166 0.498354 H 4.475774 1.701684 0.626590 H 3.874223 3.924937 0.050976 C 1.210734 1.910086 0.034499 H 0.995971 1.572629 1.056768 C 2.259780 0.393471 0.407392 C 0.973119 4.286144 0.945972 H 2.357618 1.327865 1.659165 H 1.719678 3.721253 0.965750 H 2.338108 0.759440 0.617129 H 0.959399 4.032477 2.008500 H 3.325862 3.272796 1.584918 H 3.933420 1.126124 0.940032 O 0.026218 1.877715 0.758718 C 1.052107 1.110668 0.434572 C 1.069123 0.093203 0.528152 C 2.219768 1.393867 1.162729 C 2.244593 0.622715 0.755710 H 0.179 091 0.167266 1.086743 C 3.381811 0.673477 0.931927 H 2.188982 2.192029 1.897195 C 3.404048 0.340890 0.034111 H 2.251720 1.408664 1.503624 H 4.281827 0.905747 1.492549

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324 C 4.649856 1.150613 0.2 37014 F 4.769069 2.142109 0.681801 F 5.766302 0.392109 0.125068 F 4.682150 1.742410 1.452259 C 0.316900 5.367944 0.526123 H 0.234787 6.004773 1.212181 H 0.304848 5.657126 0.522692 Z CB product ( CH 2 =CHR8) B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1192.92232270000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1192.43142626000 a.u C 0.099900 2.466952 0.808794 H 0.128084 3.529735 0.891404 C 0.511566 2.061075 0.5 81099 H 0.377003 1.959862 1.214526 H 1.047725 1.114428 0.599549 O 1.263131 3.117692 1.218035 C 1.886413 0.037820 3.667240 H 2.470405 0.878230 3.595288 C 1.239757 0.479204 2.377738 H 1.035174 1.559442 2.431721 C 0.128686 0.241805 2.136076 H 0.709346 0.120243 3.066374 C 0.061798 1.719084 1.906445 H 0.423582 2.229497 2.798625 O 2.165451 0.207749 1.333534 O 0.850996 0.360715 1.062128 C 2.153788 1.116755 0.239259 C 1.646155 1.487010 1.445569 C 3.107879 0.633226 0.829524 C 3.375955 0.730726 0.994895 C 3.697963 1.551652 1.705434 C 4.215337 1.165465 2.021885 H 2.935754 1.441702 0.303655 C 4.531309 1.117133 2.736610 H 3.507719 2.615807 1.578726 C 4.792660 0.244742 2.898023 H 4.419164 2.227001 2.136544 H 4.983288 1.843024 3.407621 H 5.445614 0.584923 3.697338 C 2.391928 1.996159 0.237797 C 3.744935 1.690634 0.051283 C 1.733569 2.768971 0.727580 C 4.428431 2.145388 1.078364 H 4.268052 1.097195 0.797687 C 2.410962 3.221215 1.859104 H 0.683970 3.017 630 0.589099 C 3.761281 2.909789 2.036435 H 5.479789 1.903705 1.208313 H 1.887832 3.819153 2.600396 H 4.291112 3.264519 2.916245 H 2.449950 2.122994 0.580896 H 1.138424 1.195057 0.172780 H 2.350985 1.185957 2.235385 H 1.007083 2.281775 1.859071 C 2.600631 3.268835 1.013639 O 3.157247 4.214320 1.519058 C 3.324438 2.224411 0.184515 H 2.844381 2.072231 0.786645 H 3.335193 1.256634 0.698974 H 4.351199 2.563992 0.044484 C 1.774949 0.679495 4.829723 H 1.212157 1.606430 4.925003 H 2.245772 0.306032 5.734686 E CB product ( CH 2 =CHR9) B3LYP/SDD/6 31G(d) SCF energy in gas p hase: 1192.92852973000 a.u. M06/SDD/6 311++G(d,p) SCF energy in solution: 1192.43492814000 a.u C 0.245536 2.052244 1.238050 H 0.597263 1.508873 1.659812 C 1.200391 2.640908 2.239879 H 0.718464 3.449852 2.802462 H 1.490408 1.878983 2.975111 O 2.354969 3.251350 1.654016 C 1.237307 1.218379 2.914351 H 2.181495 1.515165 2.460440 C 0.282401 0.496907 1.997703 H 0.448967 0.060957 2.604440 C 0.519751 1.490048 1.094244 H 0.93 1733 2.263702 1.765139 C 0.382752 2.141869 0.083491 H 1.221910 2.692483 0.502631 O 1.060866 0.412687 1.226709 O 1.589230 0.830807 0.422866 C 0.366691 1.543046 0.703538 C 2.801991 0.736086 1. 165108 C 1.368602 2.535318 0.159448 C 1.048324 3.309046 0.961662 C 2.606863 2.727485 0.784890 C 1.941188 4.267557 1.444155 H 0.093455 3.159778 1.461517 C 3.504325 3.677614 0.297721 H 2.863832 2.117024 1.644740 C 3.173263 4.453531 0.815693 H 1.677678 4.861084 2.315849 H 4.464454 3.813412 0.789072 H 3.873111 5.194359 1.193369 C 3.889917 0.202629 0.264579 C 4.634356 0.923714 0.62664 1 C 4.180166 0.848228 0.945130 C 5.657737 1.396442 0.198488 H 4.412758 1.436353 1.560172 C 5.195400 0.374830 1.773744 H 3.599778 1.719934 1.235016 C 5.939203 0.748563 1.400936 H 6.228579 2. 272846 0.096598 H 5.410413 0.883183 2.710058 H 6.732639 1.115921 2.046313

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325 H 0.342660 1.243241 0.075760 H 0.222211 2.007111 1.514744 H 2.683063 0.079484 2.039978 H 3.071210 1.736458 1.543836 C 3.442370 2.522344 1.253516 O 4.333665 3.107395 0.687226 C 3.468175 1.034549 1.540866 H 3.354260 0.822175 2.609364 H 2.666608 0.517973 1.002143 H 4.431321 0.650067 1.204726 C 0.984890 1.505276 4.190900 H 0.057108 1.207416 4.676181 H 1.697669 2.049533 4.803911