Methodological Development and Computational Investigations of Metal-Catalyzed Coupling Reactions Citation Anderson, Robert Lon (2026) Methodological Development and Computational Investigations of Metal-Catalyzed Coupling Reactions. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/zr3d-vz73. https://resolver.caltech.edu/CaltechTHESIS:11172025-045827404 Abstract Chapter One describes the computational study of the asymmetric arylation of propargylic electrophiles. While previous mechanistic experiments have verified the general scheme of the catalytic cycle, it was still not known what the enantiodetermining step is, or how factors of the ligand and substrate influence reactivity. To answer these questions, a computational study to emulate the entire catalytic cycle was performed. It was determined that radical addition to the nickel catalyst was likely the enantiodetermining step. While the standard substrate and ligand combinations result was well predicted, the computational method was not widely applicable to different ligands. This implies that the catalytic cycle may not go through a discrete radical capture and reductive elimination step, but instead a more concerted process may be operating. Chapter Two details the development of the asymmetric cross-coupling between tertiary nucleophiles and secondary electrophiles. Specifically, α-zincated benzylic nitriles are asymmetrically coupling with secondary alkyl iodides under the influence of a nickel catalyst and iminopyrox ligand. This study represents the first report of such a ligand being use for any asymmetric nickel-catalyzed cross-couplings. Chapter Three describes computational work on three separate projects published by coworkers in the Fu lab. 1) The first section details work on the nickel-catalyzed asymmetric coupling of enynes with secondary racemic electrophiles to accomplish for the first time the simultaneous control of axial and point chirality. The computational work probed the possible steps of rearrangement of the putative nickel-propargyl species into nickel allenyl species, as well as rationalized the different reactivity of the catalyst towards different electrophiles. 2) The second project was investigations into the photocatalytic coupling of secondary and tertiary electrophiles with secondary amines by copper and a dual-ligand system. The computations shed light on possible C—N coupling mechanisms, as well as rationalized the differing photoactivity of the two CuI complexes present in the system. 3) The final work supported mechanistic studies into the photocatalytic asymmetric azidation of α-bromoamides by a copper-phosphine complex. DFT studies were performed to predict EPR spectra which were used to disambiguate the possible CuII species present in solution. Item Type: Thesis (Dissertation (Ph.D.)) Subject Keywords: Asymmetric Catalysis, carbon-carbon bond fromation, nickel catalysis, DFT studies, mechanistic studies, quaternary stereoecenters Degree Grantor: California Institute of Technology Division: Chemistry and Chemical Engineering Major Option: Chemistry Thesis Availability: Public (worldwide access) Research Advisor(s): Fu, Gregory C. Thesis Committee: Reisman, Sarah E. (chair) Agapie, Theodor Goddard, William A., III Fu, Gregory C. Defense Date: 30 September 2025 Funders: Funding Agency Grant Number National Institutes of Health (NIH) 5R35GM145315-04 Record Number: CaltechTHESIS:11172025-045827404 Persistent URL: https://resolver.caltech.edu/CaltechTHESIS:11172025-045827404 DOI: 10.7907/zr3d-vz73 Related URLs: URL URL Type Description https://doi.org/10.1021/jacs.4c00593 DOI Article adapted for chapter 3 https://doi.org/10.1038/s41557-024-01692-w DOI Article adapted for chapter 3 https://doi.org/10.1021/jacs.5c10003 DOI Article adapted for chapter 3 ORCID: Author ORCID Anderson, Robert Lon 0009-0000-5568-7768 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 17764 Collection: CaltechTHESIS Deposited By: Robert Anderson Deposited On: 09 Jan 2026 00:36 Last Modified: 09 Mar 2026 21:54 Thesis Files PDF (Redacted Thesis - ch. 2 omitted) - Final Version See Usage Policy. 3MB Repository Staff Only: item control page

Methodological Development and Computational Investigations of Metal-Catalyzed Coupling Reactions Thesis by Robert L. Anderson In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry CALIFORNITA INSTITUTE OF TECHNOLOGY Pasadena, California 2026 (Defended September 30th, 2025) ii © 2026 All rights reserved iii ACKNOWLEDGEMENTS Earning a PhD in chemistry is no doubt, one of the most difficult things I consider myself to have accomplished. In remembering the struggles, twists of fate, late nights, and flashes of insight, it cannot be forgotten that no amount of any of these would have made achieving this degree possible were it not for the myriad people who helped me with incredible thoughtfulness, companionship, support, and care. While it must be disclaimed that no short epitaph here can give full and proper credit to those who played this role, let it be said that the following work stands as a testament to not only the work described, but also those people who made it possible. First among these is my advisor, Professor Gregory C. Fu. During my studies, Greg has provided the support I have needed to develop as a chemist, as well as the guidelines needed to pursue the right lines of inquiry. He has challenged me to be an expert and shown me the indispensable nature of expertise. I greatly appreciate the risks he undertook to support my progress and for believing in my potential. His unerring professionalism displayed without coldness enabled a more honest approach to the scientific process, the benefits of which cannot be overstated. I must thank also members of my committee, Professor Sarah Reisnman, Professor Theo Agapie, and Professor Bill Goddard. Their continual willingness to pursue discussion and provide support and ideas was critical to my success. I have greatly enjoyed working with my coworkers in the Fu lab, who have provided a deep well of knowledge, friendship, and many hilarious stories. I want to especially thank Dr. Dan Tong, who pursued his degree alongside me; his innovation always provided me with inspiration, and his sense of humor proved an excellent addition to lab culture. I appreciate greatly the work of my collaborators, Dr. Jason Rygus, Dr. Asik Hossain, Dr. Feng Zhong, Dr. Hyungdo Cho, Dr. Giuseppe Zuccarello, Ruby Chen, Claudia Zhang, and Carlos Del Angel Aguilar. I want to thank iv all the other labmates whose time overlapped with mine, including Dr. Zhaobin Wang, Arianna Ayonon, Dr. Wendy Zhang, Dr. Zepeng Yang, Dr. Socrates Munoz, Dr. Suzanne Batiste, Dr. Robynne Neff, Dr. Dylan Freas, Dr. Felix Schneck, Dr. Caiyou Chen, Dr. Renhe Li, Dr. Dong Liu, Rina Wang, Grace Fleury, Yuxuan Li, Laura Martinez Leal, Kyra Jackson, Dr. Arup Mondal, Dr. Skye Yang, Matt Wong, and Zhuoyan Wang. I also have much appreciation for Julianne Just who has provided stellar support for the lab, as well as Joyce Wu for accomplishing the same. The wider Caltech community also deserves mention, including my collaborators Dr. Paul Oyala for operating the Caltech EPR facility, Ruby Chen, and Maria Blankenmeyer. Dr. Charles Musgrave provided significant support in teaching me computational techniques. Much thanks goes to Dr. Scott Virgil for providing unestimable support for lab equipment, as well as Dr. David Vander Velde and Dr. Rajan Paranji for maintaining the NMR facility. Thanks go to Nathan Hart for keeping our glassware in working order, and to Joe Drew for keeping the building in order. In addition, thank you to Leslie for keeping our floor clean tirelessly for many years. The administrative staff of Caltech deserves mention, including Alison Ross, Suri Pourmodheji, Annette Luymes, and Grace Liang-Franco, who needs special recognition for updating the periodic table of elements located on the wall of Noyes 153 at my request. Further, Suresh Gupta provided me with technical help at just the right time. My time at Caltech was also blessed with the company of many friends. I remember fondly times with my roommates Dr. Nick Watkins. Dr. Brian Lee, Dr. Michelle Chan, Dr. Steven Stradley, Andreas Butler, and Tucker Folsom. Other friends found at Caltech include Sari Kerkhove, Dr. Annette Boehme, Jillian Reed, David Fager, Vignesh Bhethanabotla, Krista Dong, Conner Wells, Dr. Jake Rothbaum, and Dr. David Cagan, Mengdi Li, and Sasha Alabugin. v Before my time at Caltech I benefited from the mentorship of many mentors and teachers, including Dr. Noam Saper at Berkeley, and my first chemistry teachers Tony Sartori and Paul Farnham who encouraged me to shoot for the stars. Thanks also to Professor Robert Zoellner, who graciously introduced me to the world of research. I am grateful to the Ammon family and the Mathews family who proved the support of critical encouragement. Without my family’s support I would never have gotten this far. My thanks go to my parents Bill and Theresa Anderson for giving me what I needed to pursue my goals. Much thanks goes to my siblings Danica, Talia, and Stephen, who have each provided key support in their own ways throughout my entire life. Thanks too to my grandmother Sue whose optimism and unconditional support cannot be discounted. Finally, I want to thank my partner, Lucia Hwang, for her unerring support during my PhD. She has always displayed understanding at the most important times, and humor when it was sorely needed. I am very excited to begin the next phase of our life together, and I hope to make many future mutual discoveries. I would also like to thank the wider Hwang family for their quick acceptance and support, and for making me feel welcome in their lives. vi ABSTRACT Chapter One describes the computational study of the asymmetric arylation of propargylic electrophiles. While previous mechanistic experiments have verified the general scheme of the catalytic cycle, it was still not known what the enantiodetermining step is, or how factors of the ligand and substrate influence reactivity. To answer these questions, a computational study to emulate the entire catalytic cycle was performed. It was determined that radical addition to the nickel catalyst was likely the enantiodetermining step. While the standard substrate and ligand combinations result was well predicted, the computational method was not widely applicable to different ligands. This implies that the catalytic cycle may not go through a discrete radical capture and reductive elimination step, but instead a more concerted process may be operating. Chapter Two details the development of the asymmetric cross-coupling between tertiary nucleophiles and secondary electrophiles. Specifically, α-zincated benzylic nitriles are asymmetrically coupling with secondary alkyl iodides under the influence of a nickel catalyst and iminopyrox ligand. This study represents the first report of such a ligand being use for any asymmetric nickel-catalyzed cross-couplings. Chapter Three describes computational work on three separate projects published by coworkers in the Fu lab. 1) The first section details work on the nickel-catalyzed asymmetric coupling of enynes with secondary racemic electrophiles to accomplish for the first time the simultaneous control of axial and point chirality. The computational work probed the possible steps of rearrangement of the putative nickel-propargyl species into nickel allenyl species, as vii well as rationalized the different reactivity of the catalyst towards different electrophiles. 2) The second project was investigations into the photocatalytic coupling of secondary and tertiary electrophiles with secondary amines by copper and a dual-ligand system. The computations shed light on possible C—N coupling mechanisms, as well as rationalized the differing photoactivity of the two CuI complexes present in the system. 3) The final work supported mechanistic studies into the photocatalytic asymmetric azidation of α-bromoamides by a copper-phosphine complex. DFT studies were performed to predict EPR spectra which were used to disambiguate the possible CuII species present in solution. viii CONTRIBUTIONS TO PUBLISHED WORK 1) A. Hossain, R. L. Anderson, C. S. Zhang, P.-J. Chen, G. C. Fu*. Nickel-Catalyzed Enantioconvergent and Diastereoselective Allenylation of Alkyl Electrophiles: Simultaneous Control of Central and Axial Chirality. J. Am. Chem. Soc. 2024, 146, 71737177. DOI: 10.1021/jacs.4c00593. Personal Contribution: I calculated bond dissociation energies for relevant molecular species as well as performed calculations exploring putative reaction intermediates. 2) H. Cho, X. Tong, G. Zuccarello, R. L. Anderson, G. C. Fu*. Synthesis of Tertiary Alkyl Amines via Photoinduced Copper-Catalysed Nucleophilic Substitution. Nature Chemistry. 2025, 17, 271-278. DOI: 10.1038/s41557-024-01692-w Personal Contributon: I calculated putative catalytic cycles to explain the C-N bond forming step, rationalize observed species in solution, and offer explanations for photocatalyst activity. 3) F. Zhong, R. L. Anderson, P. H. Oyala, G. C. Fu*. Photoinduced, Copper-Catalyzed Enantioconvergent Azidation of Alkyl Halides. JACS. https://doi.org/10.1021/jacs.5c10003 Personal contribution: I performed calculations of EPR properties of putative species to help disambiguate the assignment of EPR spectra of the catalytic reaction. ix TABLE OF CONTENTS Copyright ........................................................................................................................................ ii Acknowledgements ........................................................................................................................ iii Abstract .......................................................................................................................................... vi Contributions to Published Work ................................................................................................. viii Table of contents ............................................................................................................................ ix List of Abbreviations..................................................................................................................... xii Chapter One: Theoretical Studies of Asymmetric Propargylic Arylation ................................. 1 Introduction ...................................................................................................................................1 1.1 Models of Asymmetric Induction ..........................................................................................1 1.2 Modeling enantioselectivity in nickel-catalyzed cross-couplings .........................................8 1.3 Motivation for the present study ..........................................................................................12 2. Computational results ................................................................................................................15 2.1 Benchmarking with crystallographically characterized compounds ...................................15 2.2 Probing the enantiodetermining step ...................................................................................16 2.3 Geometric description of the radical determining step ........................................................18 2.4 Geometry of the NiIII intermediate .......................................................................................19 2.5 Geometry of the reductive elimination step ........................................................................19 2.6 Enantioselectivity predictions of alternative substrates .......................................................20 2.7 Time course ..........................................................................................................................24 3. Experimental procedures ...........................................................................................................25 3.1 General information ............................................................................................................25 3.2 Synthesis of electrophiles ....................................................................................................25 3.3 Synthesis of ligands ............................................................................................................29 3.4 Synthesis of the nucleophile ...............................................................................................39 4. Computational Details ..............................................................................................................39 4.1 General information ............................................................................................................39 x 4.2 Computational data .............................................................................................................41 4.2.1 Data and structures for comparisons with known crystal structures ............................41 4.2.2 Calculated structures for the catalytic cycle ................................................................50 4.2.3 Transition state structures for radical additions ............................................................73 5. References ................................................................................................................................172 Chapter Two: Asymmetric Coupling of Tertiary Nucleophiles with Secondary Electrophiles 1. Introduction ..............................................................................................................................183 2. Reaction optimization ..............................................................................................................190 2.1 Coupling of primary electrophiles with tertiary nucleophiles ...........................................190 2.2 Coupling of secondary electrophiles with tertiary nucleophiles ........................................191 2.2.1 Effect of selected reaction parameters .......................................................................192 2.3 Scope of coupling tertiary nucleophiles with secondary electrophiles ..............................196 2.4 Mechanistic observations ...................................................................................................197 2.4.1 Effects of using cyclohexyl bromide as an additive ..................................................197 2.4.2 Time course using Ni(COD)2 as a precatalyst ............................................................199 2.4.3 IR-spectroscopy of the nucleophile solution ..............................................................200 3. Procedures ................................................................................................................................202 3.1 General information ..........................................................................................................202 3.2 Substrate synthesis .............................................................................................................202 3.2.1 Synthesis of nitriles .....................................................................................................202 3.2.2 Synthesis of α-chloronitriles .......................................................................................208 3.3 Ligand synthesis.................................................................................................................217 3.3.1 Synthesis of oxazolines ...............................................................................................218 3.3.2 Cross-coupling of oxazolines ......................................................................................220 4. Asymmetric alkylation of α-zincated nitriles ..........................................................................221 5. NMR spectra of selected compounds ......................................................................................230 6. References ................................................................................................................................248 xi Chapter Three: Compiled Computational Investigations ............................................................ 1. Enantio- and disastereoselective allenylation of alkyl electrophiles .......................................256 1.1 Background ........................................................................................................................256 1.2 Calculations of NiII hydride species ...................................................................................258 1.3 Calculations of L*NiII—propargyl species ........................................................................259 1.4 Calcultions of L*NiBr—allenyl species ............................................................................260 1.5 Estimation of bond dissociation energies .........................................................................261 1.6 Computational details ........................................................................................................263 1.6.1 General methods .........................................................................................................263 1.6.2 Geometry of calculated species .................................................................................264 2. Copper-catalyzed C—N coupling ............................................................................................299 2.1 Background ........................................................................................................................299 2.2 Computational investigations of the photocatalysts ..........................................................300 2.3 Computational investigations of the C—N coupling step .................................................302 2.4: Computational details .......................................................................................................306 2.4.1 General methods .........................................................................................................306 2.4.2. Calculated structures ..................................................................................................307 3. Copper-catalyzed asymmetric azidation of alkyl halides ........................................................344 3.1 Background ........................................................................................................................344 3.2 EPR calculations of CuII-azide species .............................................................................345 3.3 Computational details ........................................................................................................346 3.3.1 Computational methods ..............................................................................................346 3.3.2 Calculated structures ..................................................................................................347 4. References ................................................................................................................................357 xii LIST OF ABBREVIATIONS %ee 2,2-bipy 2-Me-THF 4CzIPN Å Ac AI Ar BArF4 BDE BDFE Biox Bn Boc BOX COD Cy DCM DFT diglyme DMA DME DMF dtbpy EPR Et Et2O EtOAc EWG FID GC GCMS glyme HBD HTE i-Pr IR kcal LED LG LiHMDS Enantiomeric excess 2,2'-Bipyridine 2-methyl tetrahydrofuran 1,2,3,5-Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, 2,4,5,6-Tetrakis(9Hcarbazol-9-yl) isophthalonitrile Angstrom Acetyl Artifical Intelligence Generic aryl group Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate Bond Dissociation Energy Bond Dissociation Free Energy Bi-oxazoline Benzyl, PhCH2 tert-butyl caraboxy group Bisoxazoline 1,5-Cyclooctadiene Cyclohexyl Dichloromethane Density Functional Theory bis(2-methoxyethyl) ether N,N-dimethylacetamide 1,2-Dimethoxyethane N,N-dimethylformamide 4,4'-di-tert-butyl-bipyridine Electron Paramagnetic Resonance Ethyl, CH3CH2 Diethyl Ether Ethyl acetate Electron Withdrawing Group Flame Ionization Detector Gas Chromatography Gas Chromatography-Mass Spectroscopy 1,2-Dimethoxyethane Hydrogen Bond Donor High-Throughput Experimentation Isopropyl fragment, (CH3)2CH Infrared kilocalori Light Emitting Diode Leaving Group Lithium hexamethyldisilylamide xiii M Me MeOH MHz ML MLR mmol mol Ms mtorr N3 NaDA n-Bu n-BuLi NMR ºC Ph ppm PTFE PyBox s-BuLi SOMO TBS t-Bu TD-DFT TFA THF TMEDA TMS TMSN3 TMTAU ΔΔG Molar Methyl, CH3 Methanol Megahertz Machine Learning Multivariate Linear Regression millimole mole Mesylate millitorr Azidyl Sodium diisopropylamide Linear n-butyl, CH3CH2CH2CH2 n-butylithium Nuclear Magnetic Resonance Degrees Celsius Phenyl, C6H5 parts per million Perfluorotetrafluoroethylene Pyridine-bisoxazoline sec-butyllithium Singly Occupied Molecular Orbtal Tert-Butyldimethylsilyl tert-Butyl Time-Dependent Density Functional Theory Trifluoroacetate Tetrahydrofuran N,N,N′,N′-Tetramethylethane-1,2-diamine Trimethylsilyl Trimithylsilyl azide N,N',N',N''-Tetramethyl-2,6,10-triazaundecane Change in the difference of Gibb's free energies 1 CHAPTER ONE 1. Introduction 1.1: Models of asymmetric induction A defining feature of the evolution of synthetic organic chemistry is the development of ever more accurate models capable of explaining and anticipating reaction outcomes. The utility of models extends beyond facilitating synthesis: their success or failure itself is a test of their foundational theories. Models can be placed on a spectrum ranging from the empirical, relying on rules derived from observations of many examples to the ab initio, those models derived from more fundamental physical laws. The development of empirical models is often top-down, involving the aggregation of data to detect trends. By contrast, the development of ab initio models by definition arises from more fundamental physical laws. The former models tend to be motivated by explaining some subset of chemical reactivity, while ab initio models attempt to explain a broad class of phenomena from a few laws. In the 19th century, empirical models dominated and include Markovnikov’s rule1, Zaitsev’s rule,2 Hoffman’s rule,3 and Walden’s observations of Figure 1.1.1: Early empirical rules for predicting product selectivity. 2 stereochemical inversion (Fig 1.1.1).4 The advent of the Schrödinger equation and related developments in quantum mechanics from 1925 marked an explosion of ab initio chemical modeling.5,6 Shortly after its introduction molecular orbital theory offered a new and powerful way to interrogate the nature chemical bonds.7 This theory in turn led to, among many other things, the Woodward-Hoffman rules, which stand as a tremendous success in the use of theory to predict stereochemical outcomes.8 Reactions involving asymmetric induction and stereoselectivity are of particular importance to organic chemists. Early attempts to solve these problems were greatly aided by the advancement of X-ray crystallography techniques alongside quantum theories, which allowed for unprecedented knowledge of the ground-state geometry of molecules. Given however that transition states, and not ground states, are of much more importance to reaction outcomes, early models were more empirical, and it had to be assumed that transition states resembled reactants. Despite this, early success was achieved in the prediction of nucleophilic additions to carbonyl compounds. Additions to carbonyl compounds represent a diverse and powerful method of C—C bond construction, and are relevant to diverse total synthesis, such as that of polyketide natural products.9 Cram,10 Felkin,11 Ahn,12 Prelog,13 and others14 provided pioneering models to explain the stereoselectivity of 1,2 additions to carbonyl compounds (Fig. 1.1.2). These models were expanded to explain additions to β-substituted carbonyls,15 as well as those with chelating β-groups.16,17 Advances in RM RL Nu O RS H Nu - - RS H RL favored Felkin-Ahn Model ‡ Nu RM RS O O RM H RL disfavored Nu H RM OH RL RS major + RM H Nu OH RL RS minor Figure 1.1.2: Felkin-Ahn stereochemical model for predicting 1,2-carbonyl addition products. 3 computing allowed for more advanced modeling and expansion of these findings.18 For example in 1982, using ab initio methods Houk reported on the preferred angles of attack of nucleophiles, electrophiles, and radicals to double bonds,19 building on the findings of Bürgi and Dunitz regarding the preferred angle of attack towards carbonyl compounds.20,21 Force field models, which essentially treat molecular bonds as springs with empirically defined spring constants,22 proved to be a valuable early application of computational chemistry, as they can provide more quantitatively accurate results while being computationally tractable.23 This has allowed for the prediction of reaction products in more complex cases. As an example, Tareda and Yamamura were able to predict the outcome of the cope rearrangement of germacrene A using a force field model, correctly predicting that only the cis-elemene isomer would form (Fig. 1.1.3A).24 Force-field models were also used to predict the selectivity of an intermolecular diels-alder reaction to generate intermediates relevant to the synthesis of the spirotetronate polyketide class of natural products(Fig (A) Me Me H Me cope rearrangement ∆ Me germacrene A Observed Predicted Me H Me H Me H Me cis-elemene H Me trans-elemene 100% >99.9% 0% <0.01% H H (B) Me Me diels-alder cyclization Et2AlCl ° ° -78 C → 23 C O Observed Predicted H H H CHO Me 1 100% >99.9% H CHO Me 2 0% <0.01% Figure 1.1.3 (A) Prediction of the major product of the cope rearrangement of germacrene A. (B) Prediction of the major product in an intramolecular diels-alder cyclization. 4 1.1.3B)25,26. Such models continue to find use, especially in systems with a very large number of atoms and in material chemistry.27,28 Force fields rely on many empirically determined parameters, and it is critical to choose the correct force field for a specific molecular system. This limits their general applicability. Ab initio quantum mechanical methods capable of interrogating general molecular systems became available in the 1990s.29–33 Most prominent of these methods is Density Functional Theory (DFT), for which the 1998 Chemistry Nobel Prize was awarded to Walter Kohn and John Pople.34–36 Usage of DFT to study chemical reactions can be divided into three somewhat overlapping categories.37 The first and most straightforward is the direct modeling of putative transition states. The second is to make use of multivariate linear regression (MLR) to model reactions based on molecular properties derived from DFT calculations. The third method is to use DFT calculated parameters as well as other data and apply machine learning to predict novel reaction outcomes.38–40 Ab initio calculation of postulated transition states can be very powerful as it can directly refute or support a given mechanistic hypothesis.41 In practice, this method requires care, both to interrogate the correct mechanistic pathways, but also ameliorate some of the inherent inaccuracies to be found in DFT,42 including the self-interaction error of electrons,43 non-modeling of dispersion forces,44 and difficulty in dealing with nearly degenerate electronic states.45 These issues are particularly noteworthy in the case of transition-metal catalyzed reactions, especially those O N H CO2H O O ‡ O N O O H H R N O O H O OH O OH R+ H R synantianti-TS syn-TS R = i-Pr R = Ph 1:1 ~99:1 Observed anti:syn ratio Figure 1.1.4: Houk-List model for proline-catalyzed enantioselective aldol reactions. Calculated anti:syn ratio >99:1 1:5-1:1 H R R 5 involving radical intermediates.46 Perhaps because of these limitations, early successes were found among elucidating mechanisms of organocatalysts or Lewis-acid catalysts.47 Prominent examples include the development of the Houk-List model for the prediction of stereoselectivity for intraand intermolecular aldol reactions catalyzed by proline (Fig 1.1.4),48,49 albeit with some ambiguity for certain substrates. Noyori reported on the ab initio investigation of the amino-alcohol mediated addition of dimethylzinc to benzaldehyde using Møller-Plesset perturbation theory, a non-DFT quantum chemistry method.50,51 Because the cost of ab initio calculations increases very rapidly with the number of atoms and structures, it is often imperative to support such studies in tandem with mechanistic experiments that can rule out alternative pathways; the studies by Houk52 and Noyori53 were founded upon prior mechanistic experiments. The best use of DFT is to model reactions which cannot be otherwise disambiguated. This requisite of firm mechanistic data has spurred the development of more implicit models for use on systems for which less is known. Multivariate linear regression (MLR) is a modeling technique for the prediction of chemical reactions. It does not seek to directly model transition states; thus it is an implicit model. MLR reduces the need for mechanistic experiments, while truncating the potential for structural insight. While MLR has recently been experiencing a renaissance,54 the idea of correlating measurable molecular properties to reactivity is not new: Hammet pioneered the use of linear free energy relationships for gaining mechanistic insights and predicting reactivity.55,56 As an example, Jacobsen was able to closely correlate the enantioselectivity of salen-type expoxidation catalysts with the Hammet parameter of salen backbone substituents.57 After Hammet, other descriptors proliferated such as the steric descriptors of Taft,58 Charton,59 the Tolman cone angle,60 and others,61 as well as the electronic descriptors of Fukui,62 electronegativity,63,64 the Tolman electronic parameter,60 Mayr fugacities,65,66 and others.67,68 MLR extends this prediction approach 6 by correlating many parameters at once to predict reactivity. MLR also makes use of DFT calculations to calculate other molecular parameters such as atomic charges, dipoles, molecular geometry, and others which cannot be easily measured.54,69,70 Because there is no prerequisite for mechanistic data, MLR can used during the optimization process of methods before in-depth mechanistic studies are performed, potentially accelerating method optimization by pointing towards the most important reaction parameters. MLR has been used in good effect by Sigman to predict the enantioselectivity of chiral-phosphoric acid catalyzed nucleophilic additions to imines.71 By analyzing over 300 molecular parameters, the enantioselectivity of enamine addition to imines was predicted for novel catalyst and substrate combinations to within 0.30 kcal•mol-1 ΔΔG. In another example, Jacobsen reported the remarkable prediction of the enantioselectivity of hydrogen-bond-donor catalysts in a Mannich reaction. The model was able to predict to a high degree of accuracy the selectivity of a poorly performing squaramide catalyst, and also a superior thiourea catalyst (Fig. 1.1.5).72 While MLR approaches are more indirect than direct modeling approaches, they nevertheless can point to important factors of catalyst or substrate properties that may guide investigations into further optimization or mechanistic studies. Boc H Me N Ar OTBS N O OMe catalyst Ph O tBu O N H N H O observed %ee: 44% predicted %ee: 42% HN Ph MeO CF3 Boc CF3 tBu S CF3 Ar = pyrene H N Ar N H N H O observed %ee: 87% predicted %ee: 89% CF3 Figure 1.1.5: MLR predictions for worst and best catalyst for HBD catalyzed Mannich reaction. 7 In recent years, machine learning approaches have been extensively applied to tackle diverse problems in organic synthesis,73–75 including predicting activation energies,76 C-H activation site selectivity,77 and regioselectivity,78 as well as optimizing polymerization catalysts79 among other uses.80,81 Like MLR, machine learning also makes use of computed or measured molecular properties. However, it differs from MLR in that non-linear relationships are used with much larger data sets incorporating fewer parameters. More recently, machine learning incorporating large language models have been investigated.82 While the large data demands of machine learning can be a drawback, trained models can quickly analyze tens of thousands of reactions.83–85 Because machine learning models predict reactivity based on extensive correlative formulae, mechanistic interpretations are difficult and rare, though some efforts have been made to develop human-interpretable models.86–88 More often, machine learning approaches have been applied to automated reaction development,89,90 and ML approaches have been extensively used to optimize stereoselective transformations.91–95 A salient recent example of this approach comes from Ao, who used ML methods to predict the selectivity of an amidase enzyme for novel amide substrates towards hydrolytic desymmetrization.96 Specifically, the model was able to accurately OH CO2NH2 R OH amidase Me OH CO2NH2 exp. ∆∆ G: 1.05 exp. CO2NH2 exp. ∆∆ G: 1.01 OH ∆∆ G: 0.43 CO2NH2 Me exp. OH Br ∆∆ G: 1.53 ∆∆ G: 2.02 OH CO2NH2 Et exp. CO2NH2 CO2NH2 exp. CO2NH2 R • -1 predicted ∆∆G > 1.86 < 2.40 kcal mol OH OH CO2NH2 OH Me CO2NH2 R • -1 predicted ∆∆G < 1.86 kcal mol OH Cl exp. ∆∆ G: 2.14 ∆∆ G: 1.83 OH CO2NH2 MeO exp. Figure 1.1.6: Machine-learning binning of substrates for amidase hydrolysis. ∆∆ G: 2.28 8 bind novel substrates into low and high selectivity cases high a high degree of accuracy (Fig 1.1.6), and the authors were able to determine key structural factors for further enzyme optimization. 1.2: Modeling enantioselectivity in nickel-catalyzed cross-couplings Over the last two decades, significant progress has been realized in the asymmetric coupling of alkyl coupling partners by nickel catalysis.97–99 Progress has not only been realized with traditional cross coupling, but also reductive100,101 photocatalytic,102–104 and electrochemical methods.105–107 The success of these methods has motivated mechanistic studies which have served to greatly expand our understanding of nickel-catalyzed cross-coupling methods.108–111 However, there are fewer studies which either seek to directly model the enantiodetermining step of these transformations or otherwise predict enantioselectivity, especially while considering observations from direct mechanistic studies. Several stand-alone DFT studies of nickel-catalyzed cross-couplings have been reported. In 2011, Lin disclosed the computational investigation of the asymmetric alkylation of αhaloindanes by primary alkylzinc compounds by nickel catalysis, 112 a method previously disclosed by our group.113 In this study, a NiI-NiIII catalytic cycle was invoked based on calculated reaction energies. They postulated that reductive elimination was the enantio- and rate determining step and directly modeled the postulated transition state. While their model correctly anticipated the correct enantiomer of product, the ΔΔG error was more than 7 kcal•mol-1 and only one substrate was calculated, and therefore little can be extrapolated from these results. Similarly, Wang reported a DFT study of the doubly-diastereoselective cross-coupling secondary electrophiles and nucleophiles developed in our group.114,115 They also argued that reductive elimination was the enantiodetermining step, and predicted a ΔΔG of 3.2 kcal•mol-1 higher than reported. Ren also reported a DFT study on the asymmetric synthesis of diarylkanes,116 developed by the Reisman 9 group.117 They predict a ΔΔG of 0.8 kcal•mol-1 for the enantiodetermining step, compared to 1.8 for the measured value. Finally, Wang performed a DFT study on our previously disclosed asymmetric coupling of olefins with tertiary electrophiles.118,119 It can be argued that the complete reliance on DFT studies uncoupled from experimental observations reduced the utility of these reports. DFT predictions of enantioselectivity for nickel-catalyzed asymmetric alkylation have been done as part of a more extensive mechanistic study. This approach has its benefits, as an interplay between theoretical and experimental results can significantly simplify interpretation of the DFT results. Molander reported studies of the dual Ir/Ni photoredox mediated asymmetric coupling of benzylic trifluoroborate salts with aryl bromides,120 modeling the racemic coupling of these coupling partners using a 2,2-bipy ligand.121 Their calculations pointed towards a Ni0/NiII/NiIII cycle in which oxidative addition of Ni0 to the aryl bromide is followed by radical capture of the benzylic radical to form a NiIII intermediate, which undergoes reductive elimination to form the product. This data indicated that reductive elimination was the enantiodetermining step due to the reversibility of the radical addition, thus operating under Curtin-Hammet conditions.122 The (3 mol%) Ir[dFCF3ppy]2(bpy)PF 6 (5 mol%) 2 Br Ni(COD) L* (5 mol%) Me BF3K N R 57% 54% Me CN 62% 74% O O Bn R Me experiment: calculated: Me L* Me Me 65% 84% tBu Figure 1.2.1: Predictions of asymmetric couplings of alkyltrifluoroborates by Molander. N Bn 10 reductive elimination barriers were calculated for the chiral Biox ligand for a variety of substrates, and reasonable agreement was found with the observed ΔΔG values (Fig. 1.2.1). In addition, further calculations were performed on the diamine catalyzed coupling of homobenzylic halides with primary alkylboronates published by our group,123 and those calculations also indicated that reductive elimination was the enantio-determining step. In 2019, our group published a mechanistic study of the asymmetric arylation of αbromoketones,124 previously developed in our group.125 Evidence from this study was consistent O Me Br MgBr L*NiIIBr2 (7 mol%) ° DME, -60 C O Me O Ph exp: 90% ee calc: 86% ee Me N Ph Me L* O N Ph Figure 1.2.2: Enantioselectivity predictions for the arylation of α-Bromoketones published by our group. with a NiI/NiIII mechanism, similar to our previous study.126 DFT calculations showed that radical addition to NiII was the rate- and enantio-determining step, and the calculated ΔΔG was 1.1 kcal•mol-1, in good agreement with the experimental result of 1.13 kcal•mol-1 for a single pair of coupling partners (Fig 1.2.2). This stands in contrast to the previous Molander study, as well as the studies of Molander120 and Lin.112 More implicit theoretical methods to probe asymmetric nickel-catalyzed reactions have also had success. Recently, Bahamonde reported on the asymmetric arylation of tetrahydrofuran mediated by a chiral nickel catalyst and iridium photocatalyst.127 During the initial phases of the study, MLR both to identify the optimal catalyst, as well as determine which catalyst features were 11 (A) O HO2C (B) O Ph Me (2 mol%) Ir[dFCF3ppy]2(dtbpy)PF6 NiCl2•glyme (15 mol%) X L* (23 mol%) ( 2.0 equiv.) O K3PO4 CO2H ° 427 nm hν, 30 C X = Cl 72% ee X = Br 22% ee Me 4CzIPN (3 mol%) NiBr2•diglyme (10 mol%) L* (10 mol%) I Et3N (5.0 equiv.) OH Ph 25 mol% MgCl2 THF, blue LED, r.t exp: 90% ee calc: 56% ee O O N Bn L* N Bn tBu tBu N iPr N N L* N iPr Modeled R2: 0.84 Figure 1.2.3: (A) Asymmetric α-arylation of THF by Bahamonde. (B) MLR optimized epoxide arylation developed by Doyle. relevant to enantioselectivity, which supported further mechanistic studies which explain the strong halide effect observed. While no direct modeling of the enantiodetermining step was made, this study serves a strong example of how implicit methods can support mechanistic studies (Fig. 1.2.3A). As another example, a recent study by Doyle used MLR methods to determine the best ligand for the asymmetric arylation of epoxides via dual photoredox and nickel catalysis.128 While the model has a relatively high R2 of 0.84 when predicting ΔΔG, in the explicitly modeled case with a substrate, the predicted %ee was significantly lower than observed (Fig 1.2.3B). More intense modeling to discover novel reactivity has been reported using artificial intelligence (AI) driven optimization supported by high-throughput experimentation (HTE). In 2024, the Liao group reported the development of a family of asymmetric nickel-catalyzed cross couplings through an AI approach.129 A combination of literature reported data as well as HTE-acquired data was used, and a predictive model was trained using only parameters describing the ligand and substrate served as input. The resultant model was able to predict ΔΔG values with a mean-average error of 12 only 0.199 kcal•mol-1, and an R2 of 0.844 when tested against literature results. The model was then used to predict the most promising ligands to accomplish the asymmetric hydroarylation of cyclic α,β-unsaturated amines in good yield and enantioselectivity with a minimum of screening. This showcases the utility of AI-driven models for the discovery of novel reactivity. 1.3: Motivation for the present study Despite these successes in the literature for analyzing and predicting enantioselectivity in asymmetric nickel-catalyzed coupling reactions, there remains a lack of studies which (A) NiCl2•glyme (3.0 mol%) R' 3.9% L* Ar ZnEt ° glyme, -20 C 2.0 equiv. R' Br R O Ar O N N N R L* (B) LNiI Br I-4 Ar Br P E LNiII Br LNiII I-3 Ar R Br [LNi II I-2 Br ZnAr2 I-1 Ar]Br ZnArX Figure 1.3.1: (A) Asymmetric alkylation of propargylic bromides reported by our group. (B) Mechanistic cycle supported by our group’s later mechanistic study. 13 systematically study a selection of ligands and substrates to elucidate the most important factors governing the enantioselectivity from an explicit modeling approach. Therefore, our group sought to fill this gap in the literature. In 2008, we published the asymmetric nickel-catalyzed arylation of propargylic electrophiles using in-situ generated arylzinc reagents (Fig 1.3.1A).130 Following this in 2014, our group performed a mechanistic study of this reaction, in which the catalytic cycle shown in Figure 1.3.1B was proposed. For simplicity, each step is drawn as irreversible.126 The mechanistic study consistent with the evidence starts with the formation of chain-carrying metalloradical I-4, likely formed by a combination reduction-disproportionation sequence.131 This radical can abstract a bromide atom from the electrophile E to generate organic radical R and nickel species I-1, which can undergo transmetalation with the arylzinc nucleophile to generate the cationic resting state I-2. The resting state can then capture a radical R to form complex I-3, which undergoes rapid reductive elimination to form the product P and regenerate metalloradical I-4. While this mechanistic study was extensive, it could not answer two fundamental questions about the reaction. The first is which step is the enantiodetermining step. There are two possibilities for which step is enantiodetermining: 1) Radical addition is reversible, and reductive elimination governs enantioselectivity under Curtin-Hammet conditions. 2) Radical addition is irreversible and is thus the enantiodetermining step. The second more general inquiry was what factors of the ligand are most important for governing enantioselectivity. The present study seeks to shed light on these questions. Given that much was known about the reaction, including crystallographic characterization of the resting state, an explicit DFT approach was seen as most appropriate. The two phases of the project would be to first find a computational method that could generate results consistent with the mechanistic 14 study and observed enantioselectivity. After this, a selection of ligands and substrates would be synthesized and subjected to the reaction conditions, as well as modeled computationally to check for agreement of the model against diverse conditions. The degree to which the model agreed with the observed results could then be used as a measure of its validity, and in turn could be probed to learn more about which factors of the ligand and substrate govern enantioselectivity. 15 2. Computational results 2.1: Benchmarking with crystallographically characterized compounds 1 L1NiI-Ph O N1 i-Pr Npy NiI 3 L1NiIIBr2 F [L1Ni -Ph][BAr 4] O O N2 Npy N1 i-Pr NiII i-Pr L1NiI-Ph Bond 2 II O O N2 II N i-Pr i-Pr F Bond N1 Ni N2 Ni 1.934 1.940 N2 Ni 1.892 1.920 NPy Ph Ni Ni 1.934 1.896 1.880 1.900 NPy Ph Ni Ni 1.898 1.881 1.930 1.880 N1 Ni Crystal Calculated (Å) (Å) 1.900 1.930 N NiII Br1 Br2 i-Pr L1NiIIBr2 [L1Ni -Ph][BAr 4] Crystal Calculated (Å) (Å) 1.906 1.910 O Npy Bond N1 Ni Crystal Calculated (Å) (Å) 2.135 2.160 N2 Ni 2.133 2.180 NPy Br1 Br2 Ni Ni Ni 1.991 2.389 2.421 2.040 2.440 2.450 Figure 2.1.1: Comparison between crystallographically characterized nickel species and their computed structures. Structures computed at the B3LYP/D4 -CPCM-DEF2-SVP/DEF2QZVPPD (on Ni) level of theory. To begin modeling the steps of the catalytic cycle, the computational methods were first benchmarked by examining how closely they came to predicting known crystallographic structures relevant to the catalysis. Figure 2.1.1 shows the comparison between the computed and crystallographic bond lengths of three nickel species. In general, the structures were well-reproduced and in most cases the bond length deviations were less than 0.3 Å. In addition, since solid-state crystallographic structures will differ somewhat in reality from the structure of solvated species, some variation would be expected even given perfect accuracy. 16 2.2: Probing the enantiodetermining step TMS Br n-Bu racemic (E1) 3.0 mol% NiBr2•DME TMS 3.9% (S)-i-Pr-Pybox (L1) Zn F F DME, -20 oC 1.6 equiv. F n-Bu 82% ee Figure 2.2.1: Reaction conditions used for modeling of the catalytic cycle. To most closely hew to the conditions used in the in-depth mechanistic study, bis(4fluorophenyl)zinc was chosen as the nucleophile, and (S)-i-Pr-Pybox was (L1) chosen as the ligand, along with the standard electrophile E1. Figure 2.2.1 shows the catalytic conditions modeled. Note that, for the (S)-ligand, the major product is the (S) product. The energetic overview of the catalytic cycle as computed is shown in Figure 2.2.2. A complete energy diagram of the Radical Addition Reductive Elimination S1 NiI+Product Adduct NiIII Intermediate Figure 2.2.2: Calculated catalytic cycle. catalytic cycle can be found in the appendix. The barrier to radical addition was found to be 10.7 and 10.6 kcal•mol-1 for the (R)-product pathway and (S)-product pathway respectively. After radical addition, the resultant NiIII complex undergoes rearrangement to a pseudo octahedral geometry, where the propargyl fragment binds to the nickel center in an η3 configuration. This 17 complex is computed to be energetically downhill from the starting NiII center and radical precursor. This species can undergo reductive elimination with barriers of 4.9 and 6.5 kcal•mol-1 for the R and S product pathways, respectively. The resultant NiI species forms an η2 adduct with the product, which presumably can be displaced with a bromide ion to generate the NiI bromide species implicated in halogen atom abstraction step. The computed barriers to radical dissociation are 19.9 and 17.4 kcal•mol-1 for the R and S pathways, respectively. This indicates that radical addition is irreversible, which shows that radical addition, and not reductive elimination, is the enantio-determining step. Further, this implies that radical addition is also the rate determining step, a hypothesis which is consistent with observations. Under the reaction conditions studied, the product is formed with an enantiomeric excess of 82%, which corresponds to a ΔΔG between the R and S pathways of 1.2 kcal•mol-1 This is in reasonable agreement with the computed value of 1.1 kcal•mol-1. 18 2.3: Geometric description of the radical-capture step (R)-Radical Addition H (S)-Radical Addition O N nBu TMS i-Pr TMS O N N i-Pr H nBu Figure 2.3.1: Calculated geometries of the radical addition transition state. It is worth examining the geometry of the radical capture step in attempt to determine which interactions have the most impact on enantioselectivity. Figure 2.3.1 shows the configuration of the minimum energy radical addition transition states for the minor-product generating (R) radical addition (left) and the major-product generating (S)-radical addition (right). Comparing the Newman projections of each transition state looking along the forming Ni-C bond with the quadrant diagram, the (S) transition state ideally places the small hydrogen atom towards the blocked quadrant. By comparison, the (R) transition state positions the TMS-alkyne group nearby to the i-Pr group of the ligand, introducing a steric clash. The length of the Ni-C bond in 19 each transition state is very similar, with 2.309 Å for the (R) transition state, and 2.314 Å for the (S) transition state. 2.4 Geometry of the NiIII intermediate (R) (S) Figure 2.4.1: Calculated geometries of the NiIII intermediate. Figure 2.4.1 shows the calculated geometries of the NiIII state for the (R) and (S) pathways. After radical addition, the complex rearranges from a square pyramidal geometry to a pseudooctahedral geometry. The propargyl fragment curves around the nickel center to bind in an η3-fashion, while the aryl ring moves from an equatorial to an axial position. The energetic difference between these isomers is 1.36 kcal•mol-1, and in this case the (R) isomer is more stable. This can be attributed to the orientation of the n-butyl group; in the (R) case it is on the opposite side of the oxazoline isopropyl group, while in the (S) case it is oriented towards it. 2.5: Geometry of the reductive elimination step Figure 2.5.1 shows the calculated geometries of each reductive elimination step. As noted in the overall energy diagram, the (R) reductive elimination has an energy barrier of 6.50 kcal•mol1 , and the (S) reductive elimination has a barrier of 4.89 kcal•mol-1. Were reductive elimination the 20 (R)-Reductive Elimination TS Geometry (S)-Reductive Elimination TS Geometry Ni-C 2.099 Ni-Ar 1.995 2.081 C-Ar ° C-Ni-Ar ∠ 61.02 Ni-C 2.106 Ni-Ar 1.996 2.058 C-Ar ° C-Ni-Ar ∠ 60.17 Figure 2.5.1: Calculated geometries of the (R) and (S) reductive elimination steps. enantiodetermining step, the opposite orientation would be obtained. Given the lower barrier of reductive elimination compared to radical dissociation (19.9 and 17.4 kcal•mol-1 for (R) and (S), respectively), the radical addition step is irreversible under the reaction conditions. This is consistent with mechanistic observations that the resting state is the NiII species. 2.6: Enantioselectivity predictions of alternative substrates To determine the applicability of the computed reaction model as well as interrogate which factors were most important for determining the enantiomeric excess of the reaction, computations were also performed which varied the electrophile and ligand used in the catalysis. The test series of ligands included those varying in steric bulk on the oxazoline ring (L1-L5), those varying in donating groups on the pyridine ring (L6-L10), and those with bis-substituted oxazoline rings (L11). For each ligand, two electrophiles were chosen, E1 with a longer n-butyl chain, and 21 TMS Br F R N i-Pr L1 O N Me i-Pr ∆∆G observed (calculated) in kcal•mol-1 O N N E1: 1.21 (1.11) E2: 1.38 (1.71) O N L2 N E1: 1.14 (0.55) E2: 1.11 (1.15) Me t-Bu O N N L5 O N i-Pr E1: 1.34 E2: 1.86 (-0.63) O E1: 0.85 (1.45) E2: 1.24 (1.68) CF3 O i-Pr L91 N tBu Ph N i-Pr i-Pr L7 E1: 0.99 (1.91) E2: 1.16 (2.06) N O N N N L4 Ph E1: 1.01 (1.04) E2: 1.24 (1.44) Me O O N O N L8 N i-Pr i-Pr E1: 1.11 (1.31) i-Pr E2: 1.31 (1.56) tBu O N N N L3 E1: 1.27 (1.81) E2: 1.42 (1.72) O N L6 O NMe2 N N O N OMe O R 1.6 equiv. O N F DME, -20 oC F racemic E1: R=nBu E2: R= Me O 3.0 mol% NiBr2•DME TMS 3.9% L* Zn O N N E2: 1.24 (1.90) N i-Pr i-Pr O L10 N E1: 1.19 (0.66) E2: 1.14 (1.83) i-Pr Me Me i-Pr O N N L11 O N E1: 0.68 (1.19) E2: 0.72 (1.02) Me Me i-Pr Figure 2.6.1: Enantioselectivities achieved for different electrophile and ligand combinations. 1 L9 was run using 20 mol% ligand to achieve maximum enantioselectivity. Each result is the average of two experiments. E2 with a simple methyl substituent. In general, E2 provided higher enantioselectivities and this provided a consistent trend to compare with the predicted results. Figure 2.6.1 summarizes both the measured ΔΔG values (in kcal•mol-1), as well as the predicted values based on computation in brackets. While a transition state could not be located for each collected data point, the data indicates that the present model of the catalytic system may not be correct, and as made cannot predict the enantioselectivity of the coupling reaction. For many reactions, the direction of change 22 ΔΔG Predictions Electrophile 1 2.5 Electrophile 2 2 1.5 1 0.5 0 -0.5 -1 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 Predicted ΔΔG (kcal•mol-1) Figure 2.6.2: Plot of predicted ΔΔG values (x axis) versus the experimental values (y axis). in enantioselectivity in moving from E1 to E2 is captured, but for many it isn’t (L3, L5, L10, L11), and in one case the sense of the enantioselectivity was totally reversed (L5). Figure 2.4.2 summarizes these results. In certain cases, it is possible that a more thorough conformer search may improve results, such as in the case of L10, as the bulky t-butyl group on the para position may further block the major transition state, and another approach may be more favorable. It is unlikely however that such effects would impact the accuracy to this degree. Another possible explanation is that, for different ligands, the mechanism changes, and reductive elimination becomes the enantiodetermining step. However, calculations on previous iterations of computational theory showed little variation in the relative energetics of the radical capture and reductive elimination steps, rendering this possibility less likely. Another possibility is that the C—Ar bond forming step is a concerted, inner-sphere process that does not involve a NiIII intermediate. This possibility was recently studied by Diao on the same ligand system described in the current study, albeit using primary stabilized benzyl radicals and secondary unstabilized radicals.132 Based on stereoelectronic effects, MLR analysis, photo-EPR spectroscopy, they proposed that C—Ar bond formation can occur by an inner-sphere 23 TMS R R OH N N Ni O N R H N Ni N N R R capture TMS R reductive elimination R O N H R O N TMS R TMS Ni R N Ni N Ar N R N R  concerted C C bond formation Figure 2.4.3: Computed C—C bond formation cycle (top), compared to bond formation as proposed by Diao (bottom). concreted mechanism. A cartoon of this mechanism versus the calculated inner-sphere mechanism is shown in Figure 2.4.3. This second pathway would be consistent with our previous mechanistic study126 and cannot be ruled out based on the calculations performed thus far. Future work should include a careful investigation of this inner-sphere pathway to determine if it would enable a better prediction of enantioselectivities. 24 2.7 Time course TMS Br n-Bu 3.0 mol% NiBr2•DME TMS 3.9% L* DME, -20 oC R n-Bu Zn O N i-Pr 1.6 equiv. 90% L* N i-Pr Time Course Experiment with Differing Ligands 80% R=H 70% % Yield O N R=CF3 60% R =OMe 50% R=NMe2 40% 30% 20% 10% 0% 0 200 400 600 800 1000 Elapsed Time (minutes) Figure 2.7.1: Time course experiment performed with different ligands. Yield estimated from GC analysis using 1,3,5-trimethoxybenzene as internal standard, and setting the maximum yield to 80%, corresponding to the maximum yield of the reaction. Yield variations are because of separate experiments used per time-point. To gain additional insight into ligand effects on the reaction, a time course was performed with ligands varying in the electron-richness of the pyridine ring. The scheme of the reaction and the results are shown in Figure 2.7.1. There was little variation in the rate of the reaction for most ligands, except for in the case where R=CF3 (L9), where the reaction was exceedingly slow and not complete even after 2 days. 25 3. Experimental procedures 3.1: General information THF, DME, Hexanes, Et2O, and DCM were deoxygenated and thoroughly sparged with nitrogen followed by passage through an activated alumina column in a solvent-purification system by SG Water USA LLC. DME was further dried by storage over activated 4 Å molecular sieves in a nitrogen-atmosphere glovebox. All compounds were used as purchased from commercial suppliers unless otherwise noted. 1 H, and 13C NMR spectroscopic data were collected on a Bruker 400 MHz or a Varian 500 MHz spectrometer at ambient temperature; chemical shifts (δ) are reported in ppm downfield of tetramethylsilane, using the solvent resonance as the internal standard. GCMS analysis was carried out using an Agilent 8890 GC System, equipped with an FID and an Agilent 5977B Mass Spectrometer. Enantioselectivities were determined by chiral GC analysis using an Agilent Technologies 6850 GC system equipped with a chiral Supelco Beta-Dex-120 column. 3.2: Synthesis of electrophiles O TMS H R H n-BuLi ° THF, -78 C TMS OH R General procedure for the synthesis of propargylic alcohols. This procedure was derived from the literature.130 To a flame dried, round bottom flask was added a magnetic stir bar and THF. The flask was capped with a rubber septum and placed under a nitrogen atmosphere through a needle attached to either a Schlenk line or nitrogen filled balloon. The flask was cooled 26 to -78 °C in an isopropanol-dry ice bath. To this solution, ethynyltrimethylsilane (1.0 equiv.) was added dropwise. After this, a solution of n-butyllithum in hexanes was added dropwise (1.05 equiv.). The solution was allowed to stir for 5 minutes, then neat aldehyde was added dropwise. The solution was allowed to gradually warm to room temperature. The reaction was then carefully quenched with a saturated ammonium chloride solution. A reaction was then concentrated under reduced pressure to remove most of the THF solvent. The resulting residue was extracted with dichloromethane (3x100 mL) using a separatory funnel. The organic solution was dried over Na2SO4, filtered, and concentrated to yield a clear yellow oil. The propargylic alcohol was then directly carried over to the next step without further purification. TMS OH nBu 1-(trimethylsilyl)hept-1-yn-3-ol. This compound was synthesized using the general procedure from ethynyltrimethylsilane (50 mmol) and n-pentanal (55 mmol). The compound was isolated as a yellow oil, and directly used in the next step without further purification. TMS OH Me 27 4-(trimethylsilyl)but-3-yn-2-ol. This compound was synthesized using the general procedure from ethynyltrimethylsilane (40 mmol) and acetaldehyde (48 mmol). The compound was isolated as a clear oil, and directly used in the next step without further purification. TMS OH R PPh3, Imidazole, Br2 DCM, r.t TMS Br R General procedure for the synthesis of propargylic bromides. This procedure was derived from the literature.130 To a flame-dried round bottom flask was added a magnetic stir bar, triphenylphosphine (1.2 equiv.), imidazole (1.2 equiv.), and DCM. A rubber septum was added, and the solution was put under a nitrogen atmosphere using either a nitrogen balloon or a Schlenk line. To this solution bromine was added by syringe dropwise (1.2 equiv.), and left to stir for 5 minutes. The propargylic alcohol dissolved in DCM was then added by syringe, and the reaction was allowed to stir at room temperature. After consumption of the propargylic alcohol, the reaction was diluted with hexanes and passed through a silica column. The column was flushed with hexanes, and the combined organic fractions were concentrated to yield a clear oil. The crude product was purified by vacuum distillation. TMS Br nBu (3-bromohept-1-yn-1-yl)trimethylsilane. This compound was synthesized from 4(trimethylsilyl)but-3-yn-2-ol (50 mmol crude) according to the general procedure. The 28 compound was purified by vacuum distillation (50°C, approx.. 150 mtorr) to yield a clear, colorless oil. (35% yield over 2 steps). The NMR spectra of the compound corresponded to the literature values.133 TMS Br Me (3-bromobut-1-yn-1-yl)trimethylsilane. This compound was synthesized from 4(trimethylsilyl)but-3-yn-2-ol (40 mmol crude) according to the general procedure. The compound was purified by vacuum distillation (~40 °C, approx. 150 mtorr) to yield a clear, colorless oil (5.05 g, 62% yield over 2 steps). The NMR spectra of the compound corresponded to the literature values.133 29 3.3: Synthesis of ligands N N R (20 mol%) ZnCl2 amino alcohol (2.0 equiv.) R O PhMe, ∆ N N O N R' N R' General Procedure 1: To a flame-dried round-bottom flask was added a large stir bar, zinc chloride, pyridine dinitrile, and amino alcohol. To this was added toluene to make a 0.1 M solution, and the mixture was heated at reflux until consumption of the starting material. The reaction was cooled to room temperature. The solvent was removed under reduced pressure, and the residue was directly purified with flash chromatography. O O N N N t-Bu t-Bu 2,6-bis((S)-4-(tert-butyl)-4,5-dihydrooxazol-2-yl)pyridine. The title compound was synthesized by general procedure 1 from pyridine-2,6-dicarbonitrile (1.00 g, 7.74 mmol) and (S)-2-amino-3,3dimethylbutan-1-ol (1.80 g, 15.48 mmol). The compound was isolated by precipitating the crude mixture in DCM/EtOAC with hexanes to yield a white colorless solid. (369 mg, 14% yield). The NMR spectra of the compound corresponded to the literature values.134 O O N N N 30 2,6-bis((S)-4-phenyl-4,5-dihydrooxazol-2-yl)pyridine. The title compound was synthesized by general procedure 1 from pyridine-2,6-dicarbonitrile (1.00 g, 7.74 mmol) and (S)-2-amino-2phenylethan-1-ol (2.12 g, 15.48 mmol). The title compound was isolated by flash chromatography (ethyl acetate/hexanes) and was isolated as an off-white crystalline solid (748 mg, 26% yield). The NMR spectra of the compound corresponded to the literature values.135 Cl Cl H N i-Pr O H N N O Cl i-Pr 4-chloro-N2,N6-bis((R)-1-chloro-3-methylbutan-2-yl)pyridine-2,6-dicarboxamide. To a flame-dried round-bottom flask was added chelidamic acid (27 mmol, 5.0 g) and a large stir bar. To this was added thionyl chloride (50 mL, 680 mmol), and 5 drops of DMF. The mixture was refluxed overnight. Volatiles were removed by distillation, and the resultant residue was redissolved in chloroform (100 mL), and the solution was cooled to 0 °C in an ice bath. A solution of D-valinol (2.0 equiv, 5.60 g, 54 mmol) in chloroform (50 mL). The solution stirred at roomtemperature overnight. The volatiles were removed under reduced pressure. To the residue was added thionyl chloride (8 mL, 11 mmol), and the mixture was refluxed overnight. Excess thionyl chloride was removed under reduced pressure, and the residue was partitioned between ethyl acetate and saturated sodium bicarbonate solution. The aqueous layer was extracted with ethyl acetate (3x50 mL), and the organic fractions were combined and dried with Na2SO4. The crude mixture was purified using flash chromatography (EtOAc/Hexanes) to yield the product as a white solid (2.55 g, 23% yield). 31 The NMR spectra of the compound corresponded to the literature values.136 OMe O O N N N i-Pr i-Pr (4R,4'R)-2,2'-(4-methoxypyridine-2,6-diyl)bis(4-isopropyl-4,5-dihydrooxazole). To a 250 mL oven-dried round-bottom flask, a large stir bar and methanol (50 mL) was added. To this was carefully added small pieces of sodium metal (1.51 g, 65.6 mmol), which was allowed to stir at room temperature until all sodium was dissolved. To this solution, 4-chloro-N2,N6-bis((R)-1chloro-3-methylbutan-2-yl)pyridine-2,6-dicarboxamide (2.55 g, 6.24 mmol) was carefully added, and the solution was refluxed overnight. The reaction was cooled to room temperature, and quenched with a saturated ammonium chloride solution (~25 mL). The aqueous later was extracted with DCM (25x3 mL), and the organic layers were combined and dried with magnesium sulfate. The solvent was removed under reduced pressure, and the residue was purified using flash chromatography on silica gel (MeOH/DCM). The title compound was isolated as a white solid (414 mg, 32% yield). The NMR spectra of the compound corresponded to the literature values.134 NMe2 NC N CN 4-(dimethylamino)pyridine-2,6-dicarbonitrile. The following procedure was adapted from the literature.137 In a nitrogen-filled glovebox, a 40 mL scintillation vial was equipped with a crossshaped stir bar. To this was added 2,6-dichloro-N,N-dimethylpyridin-4-amine (1.0 g, 5.22 mmol), 32 Zn(CN)2 (674 mg, 5.74 mmol), zinc (32 mg, 0.52 mmol), rac-2-(Di-tert-butylphosphino)-1,1′binaphthyl (207 mg, 0.52 mmol) and Pd(TFA)2 (86.8 mg, 0.26 mmol). DMA was then added (20 mL). The vial was capped with a PTFE septum cap and was brought out of the glovebox and heated to 95 °C overnight. The reaction was allowed to cool to room temperature and was filtered through a pad of celite. The solvent was removed under reduced pressure, and the crude material was subjected to the next step without further purification. NMe2 O O N N N i-Pr i-Pr 2,6-bis((R)-4-isopropyl-4,5-dihydrooxazol-2-yl)-N,N-dimethylpyridin-4-amine. The title comound was synthesized according to general procedure 1 from 4-(dimethylamino)pyridine-2,6dicarbonitrile (899 mg, 5.22 mmol) and D-Valinol (1.08 g, 10.44 mmol). The crude reaction was purified by flash chromatography using silica deactivated with triethylamine (Acetone/DCM) to yield the title compound as a white solid (420 mg, 23% over 2 steps). The NMR spectra of the compound corresponded to the literature values.136 NH3OMs 33 2-Ammoniumbiphenyl mesylate. The title compound was synthesized using a procedure adapted from the literature.138 To a 100 mL round bottom flask was added a large stir bar, 2-aminobiphenyl (1.69 g, 10 mmol), and diethyl ether (30 mL). Once the amine had dissolved, a solution of methanesulfonic acid (961 mg, 10 mmol) in diethyl ether (5 mL) was added dropwise, and the mixture was stirred for 30 minutes. The reaction was then filtered, and the collected solid was washed with diethyl ether (3x10 mL). The title compound was isolated as a white solid (2.57 g, 97% yield). NH Pd O Ms 2 μ-OMs Dimer. The title compound was synthesized using a procedure adapted from the literature.138 A 250 mL round bottom flask was equipped with a stir bar, 2-ammonium biphenyl mesylate (2.57 g, 9.7 mmol) and Pd(OAc)2 (2.19 g, 9.7 mmol). The flask was equipped with a rubber septum, and the vessel was evacuated and backfilled with nitrogen three times, and the flask was equipped with a nitrogen balloon. Anhydrous toluene (40 mL) was added by syringe through the septum. The reaction was heated to 50 °C for two hours. The solution was allowed to cool and filtered. The off-white filtrate was washed with toluene and dried to yield the product as an offwhite solid (3.69 g, quantitative). The NMR spectra of the compound corresponded to the literature values.138 34 NH Pd L PtBu2 i-Pr L = i-Pr i-Pr Pd-Cat-1. The title compound was synthesized using a procedure adapted from the literature.138 A flame-dried 50 mL round bottom flask was equipped with a stir bar, μ-OMs dimer (370 mg, 0.50 mmol), and di-tert-butyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphane (424 mg, 1.00 mmol). The flask was sealed with a rubber septum, evacuated and backfilled three times with nitrogen, and equipped with a nitrogen balloon. DCM was added using a syringe ( 10 mL), and the reaction was allowed to stir at room temperature for one hour. The solvent was removed under reduced pressure, and the residue was triturated with hexanes to yield the product as a fine yellow powder (415 mg, 50% yield). The NMR spectra of the compound corresponded to the literature values.138 Me NC N CN 4-methylpyridine-2,6-dicarbonitrile. The title compound was synthesized with a procedure adapted from the literature.139 To a 100 mL round bottom flask was added a stir bar, Pd-Cat-1 (159 mg, 0.2 mmol), 2,6-dichloro-4-methylpyridine (1.62 g, 10.0 mmol), and Zn(CN)2 (1.55 g, 13.2 mmol). The flask was sealed with a rubber septum, evacuated and backfilled three times with nitrogen, and equipped with a nitrogen balloon. THF (10 mL) and degassed, deionized water (40 mL) was added. The reaction was heated to 40 °C and stirred overnight. The reaction was cooled to room temperature, and a saturated solution of NaHCO3 was added, and ethyl acetate. The 35 solution was stirred for 5 minutes. The organic later was removed, and the aqueous later was extracted with ethyl acetate (3x10 mL). The organic fractions were combined and dried over MgSO4. The solvent was removed under reduced pressure, and the residue was purified by flash chromatography (EtOAc/Hexanes) to yield the product as a white solid (1.13 g, 79% yield). The NMR spectra of the compound corresponded to the literature values.140 Me O O N N N i-Pr i-Pr (4S,4'S)-2,2'-(4-methylpyridine-2,6-diyl)bis(4-isopropyl-4,5-dihydrooxazole). This compound was synthesized according to general proceedure 1 from 4-methylpyridine-2,6-dicarbonitrile (1.13 g, 7.89 mmol) and L-Valinol (1.63 g, 15.8 mmol). The title compound was purified by flash chromatography and was isolated as a white solid (1.33 g, 53% yield). CF3 NC N CN 4-(trifluoromethyl)pyridine-2,6-dicarbonitrile. The title compound was synthesized according to a modified literature procedure.137 In a nitrogen-filled glovebox, a 40 mL scintillation vial is charged with 2,6-dichloro-4-(trifluoromethyl)pyridine (1.08 g, 5.00 mmol), Zn(CN)2 (646 mg, 5.5 mmol), zinc (65 mg, 1 mmol), rac-2-(Di-tert-butylphosphino)-1,1′-binaphthyl (199 mg, 0.5 mmol), and Pd(TFA)2 (83 mg, 0.25 mmol). To the vial was added a cross-shaped stir-bar, followed 36 by 20 mL of DMA. The vial was capped with a cap with a PTFE septum, brough out of the glovebox, and heated at 95 oC overnight. The reaction was cooled to room temperature, filtered through a plug of celite, and the solvents were removed under reduced pressure. The residue was purified by flash chromatography (Ethyl acetate/hexanes) to yield the compound as a yellow solid (596 mg, 61% yield). The NMR spectra of the compound corresponded to the literature values.137 CF3 O O N N N i-Pr i-Pr (4R,4'R)-2,2'-(4-(trifluoromethyl)pyridine-2,6-diyl)bis(4-isopropyl-4,5-dihydrooxazole). The title compound was synthesized using general procedure 1 from 4-(trifluoromethyl)pyridine-2,6dicarbonitrile (596 mg, 3.00 mmol) and D-Valinol (619 mg, 6.00 mmol). The compound was purified using flash chromatography (Acetone/DCM), and was obtained as a white solid (634 mg, 62% yield). The NMR spectra of the compound corresponded to the literature values.137 t-Bu Cl N O 4-(tert-butyl)-2-chloropyridine 1-oxide. To a 250 mL round bottom flask was added a stir bar and 4-(tert-butyl)-2-chloropyridine (5.00 g, 29.5 mmol). Following this, glacial acetic acid was 37 added (42 mL), followed by aqueous hydrogen peroxide (30% in water, 33.6 mL). The reaction was stirred at 80 °C for four hours, at which time another charge of hydrogen peroxide was added (30% in water, 33.6 mL). The reaction was further stirred overnight, then allowed to cool to room temperature. The volume was reduced by solvent evaporation under reduced pressure, then was quenched by addition of Na2CO3. The residue was extracted with DCM (50x3 mL), and the combined organic layers were dried over MgSO4, and concentrated to yield the title compound as a yellow solid, which was carried forward without further purification. t-Bu Cl N Cl 4-(tert-butyl)-2,6-dichloropyridine. To a 100 mL round bottom flask was equipped with a stir bar. To this was added 4-(tert-butyl)-2-chloropyridine 1-oxide (5.48 g, 29.5). The flask was cooled with an ice bath to 0 °C, and POCl3 was slowly added (2.30 g, 15 mmol). The reaction was then heated to reflux, and left at this temperature overnight. The reaction was then cooled to room temperature, and poured over ice. The aqueous layer was extracted with dichloromethane, and the organic layers were combined and dried with MgSO4. The solvent was removed under reduced pressure, and the residue was purified by flash chromatography (Ethyl acetate/hexanes) to yield the title compound as a white solid (3.13 g, 52% yield over two steps). The NMR spectra of the compound corresponded to the literature values.141 t-Bu NC N CN 38 4-(tert-butyl)pyridine-2,6-dicarbonitrile. The title compound was synthesized according to a modified literature procedure.139 To a 100 mL round bottom flask was added a stir bar, Pd-Cat-1 (264 mg, 0.33 mmol), 4-(tert-butyl)-2,6-dichloropyridine (1.70 g, 8.33 mmol), and Zn(CN)2 (1.29 g, 11.0 mmol). The flask was sealed with a rubber septum, evacuated and backfilled three times with nitrogen, and equipped with a nitrogen balloon. THF (10 mL) and degassed, deionized water (40 mL) was added. The reaction was heated to 40 °C and stirred overnight. The reaction was cooled to room temperature, and a saturated solution of NaHCO3 was added, and ethyl acetate. The solution was stirred for 5 minutes. The organic later was removed, and the aqueous later was extracted with ethyl acetate (3x10 mL). The organic fractions were combined and dried over MgSO4. The solvent was removed under reduced pressure, and the residue was purified by flash chromatography (EtOAc/Hexanes) to yield the product as a yellow solid (1.75 g, quantitative). t-Bu O N i-Pr O N N i-Pr (4S,4'S)-2,2'-(4-(tert-butyl)pyridine-2,6-diyl)bis(4-isopropyl-4,5-dihydrooxazole). The title compound was synthesized from 4-(tert-butyl)pyridine-2,6-dicarbonitrile (1.52 g, 8.33 mmol) an L-Valinol (1.80 g, 17.5 mmol). The crude reaction was purified by flash chromatography (MeOH/DCM) to obtain the productas a white solid (980 mg, 33%). The NMR spectra of the compound corresponded to the literature values.142 39 3.4: Synthesis of the nucleophile Zn F F Bis(4-fluorophenyl)zinc. In a nitrogen-filled glovebox, to a 40 mL scintillation vial was added a cross-shaped magnetic stir bar, followed by zinc bromide (10 mmol, 2.25), then diethyl ether (3.0 mL). A septum cap was added, and the reaction was strongly stirred. A solution of (4fluorophenyl)magnesium bromide in diethyl ether was added (2.0 M, 10 mL, 20 mmol). The reaction was allowed to stir overnight. A small amount of dried celite was added, followed by 1 mL of dioxane during strong stirring. The resulting cloudy solution was filtered through celite, and the filtrate was evaporated under reduced pressure. The residue was sublimed (105 °C, 100 mTorr) to yield the product as a slightly yellow microcrystalline product (1.10 g, 43% yield). The NMR spectra of the compound corresponded to the literature values.133 4.1 Computational Details 4.1.1: General information All calculations were performed using the Orca 5.0 software package,143–149 except in certain noted cases where the ORCA 6.10 packages was used.150 Geometry optimizations and frequency calculations were performed using the ωB97M functional151 using the D4 dispersion correction.152 Solvation effects were approximated using the conductor-like polarizable continuum model (CPCM),153 using a probe radius of 2.42 Å, a dielectric coefficient of 7.2, and a refractive index of 1.38 to approximate 1,2-dimethoxyethane.154 The basis set Def2-SVP155 was used on all 40 atoms except nickel, on which DEF2-QZVPPD was used.156 The vibrational frequencies of each species was confirmed to have no imaginary frequencies in the case of ground states, and one imaginary mode in the case of transition states.157 Single-point calculations were performed on all geometries to refine the electronic energies using the ωB97M-V functional, and the DEF2-TZVPD basis set on all atoms except Ni, on which DEF2-QZVPPD was used. Figures of computed structure were generated using the Mercury software package.158 41 4.2 Computational Data 4.2.1: Data and Structures for comparisons with known crystal structures. L1NiIPh O N1 i-Pr Npy NiI O N2 i-Pr The geometry of this species was calculated using Orca 6.10. Calculated geometry Ni1 N2 O3 N4 C5 C6 N7 C8 C9 H10 O11 C12 H13 C14 H15 H16 C17 H18 C19 H20 Atom X 0 -1.1051 -3.4249 -1.3937 1.115 -2.3858 1.0823 -2.2839 -3.1153 -4.0541 1.2769 1.5054 1.1479 -3.0197 -2.7474 -3.8748 -2.7213 -3.3552 2.4234 2.5084 Y 0 0.1146 -2.0273 -1.1652 -0.1025 -1.2796 1.202 -0.5925 -0.523 -1.0772 2.2307 1.0502 2.0317 -2.6461 -3.6894 -2.6297 0.2517 0.3131 1.7986 2.4164 Z 0 -1.5221 0.1056 0.5814 1.5356 -0.2884 -1.0711 -1.526 -2.6669 -2.6918 -3.0484 2.242 1.915 1.3477 1.1355 2.0325 -3.7399 -4.6245 -1.0181 -0.1154 42 C21 H22 C23 H24 C25 C26 H27 H28 C29 C30 H31 C32 H33 H34 H35 C36 H37 C38 H39 C40 H41 H42 H43 C44 H45 C46 H47 H48 H49 C50 H51 C52 H53 C54 H55 H56 H57 2.3434 2.6208 -1.8101 -1.0149 0.5766 2.4268 2.2731 3.3161 -0.7242 -1.4847 -1.1608 -3.2328 -3.0116 -3.3659 -4.196 3.512 3.2789 2.4595 2.8318 3.4772 2.4968 4.2283 3.7024 -2.1113 -1.1828 4.8866 5.171 5.6583 4.9084 1.6142 1.3408 2.8279 3.4856 -2.3861 -3.3006 -2.5236 -1.5531 0.9897 1.9077 -1.8172 -2.4836 1.4628 2.685 3.7475 2.5706 0.8653 0.9784 1.5923 0.1707 0.6996 0.9284 -0.3486 0.7145 0.1195 -1.4025 -2.373 -0.2167 -0.7019 -1.011 0.3174 -0.7957 -0.2139 1.3504 1.9759 0.5763 1.9823 -1.3274 -2.2573 -0.2407 -0.2938 -1.5026 -2.1139 -0.7729 -2.1643 3.3595 3.8838 1.8231 2.183 -2.2317 -2.2828 -2.0576 -2.9116 -2.5741 -3.7096 -4.5484 2.5588 1.6208 3.3438 2.4393 -0.9648 -0.0688 3.1257 3.4633 -2.1746 -2.2844 -2.0652 -3.1104 2.9339 3.0432 -0.7686 -1.6288 -0.657 0.1311 2.0147 1.5065 3.8063 4.6763 4.2596 4.2103 5.0698 4.5387 Referenced crystal structure Atom X Y Z 43 Ni1 N2 O3 N4 C5 C6 N7 C8 C9 H10 O11 C12 H13 C14 H15 H16 C17 H18 C19 H20 C21 H22 C23 H24 C25 C26 H27 H28 C29 C30 H31 C32 H33 H34 H35 C36 H37 C38 H39 C40 H41 H42 H43 0 -1.1168 -3.5902 -1.489 1.1884 -2.482 1.1458 -2.3391 -3.1585 -4.0216 1.3262 1.4994 0.9854 -3.1844 -3.0017 -3.8911 -2.6962 -3.2408 2.4214 2.2954 2.5305 2.7074 -1.9047 -1.2122 0.6418 2.5308 2.5845 3.3393 -0.6843 -1.4301 -1.1058 -3.2388 -3.0065 -3.3058 -4.0982 3.6369 3.4734 3.0065 3.5317 3.8327 2.9947 4.5364 4.091 0 0.162 -1.7159 -0.9929 -0.2011 -1.0756 1.0813 -0.4643 -0.408 -0.8056 2.0994 0.8181 1.6167 -2.3902 -3.3474 -2.3178 0.2355 0.262 1.8454 2.5762 0.7101 1.4248 -1.6628 -2.3304 1.3226 2.4912 3.476 2.1649 0.7791 0.8503 1.295 0.3481 0.8066 1.0043 -0.1103 1.0181 0.6963 -1.4743 -2.2649 -0.208 -0.7148 -0.7734 0.0747 0 -1.4929 0.2152 0.6553 1.4633 -0.2069 -1.1226 -1.4763 -2.6069 -2.5951 -3.1394 2.372 2.3525 1.4421 1.2725 2.1308 -3.7465 -4.5245 -1.0234 -0.351 3.3038 3.9046 1.8944 2.1702 -2.2886 -2.4145 -2.3376 -2.8866 -2.6108 -3.7622 -4.537 2.7012 1.8662 3.4254 2.5939 -0.605 0.3284 2.4741 2.4884 -1.4829 -1.5258 -1.102 -2.3841 44 C44 H45 C46 H47 H48 H49 C50 H51 C52 H53 C54 H55 H56 H57 -2.1575 -1.3077 4.8969 5.08 5.6606 4.7506 1.9598 1.7531 3.2996 4.0144 -2.4561 -3.2415 -2.6325 -1.684 -0.6711 -0.1632 1.904 2.243 1.3743 2.6578 -1.3686 -2.1121 -0.4482 -0.5321 -1.4376 -2.0087 -0.7998 -1.9937 3.0372 3.1822 -0.5728 -1.474 -0.2616 0.0352 1.5837 1.0294 3.3467 3.9672 4.3373 4.2068 5.0597 4.5752 L1NiIIPh[BArF4] O N1 i-Pr Npy NiII O N2 i-Pr The geometry of this species was calculated using Orca 6.10. Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 Atom X 0 -2.7273 2.9307 -1.5364 0.1065 1.5678 -2.5046 Y 0 -2.1652 2.0132 -1.1213 -0.08 1.0981 -1.9137 Z 0 1.909 1.7687 0.3328 1.9178 0.2528 -0.444 45 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 -3.0515 -3.4396 -4.3968 -3.6186 -1.732 -0.8042 -0.7708 -1.5159 0.2585 0.32 1.2107 2.0148 1.0885 1.9018 3.5009 4.4551 3.6792 2.4453 2.9101 -1.7941 -1.1083 -0.9656 -0.2054 -0.4393 -1.5934 -2.8039 -2.2907 -3.3666 -3.5274 1.6481 0.8894 2.5539 3.3429 1.9715 3.0389 0.9267 0.2339 0.3366 1.6325 -0.103 -1.2471 -2.1002 -1.3259 -1.2433 -2.4485 -1.917 -3.5275 -1.3775 -0.7871 -0.8765 -1.4537 -0.195 -0.2417 0.5448 1.077 0.5733 1.2503 2.4034 1.8742 3.4828 1.9596 1.3531 -2.9835 -2.4248 -3.949 -3.422 -4.6628 -4.5364 -3.7128 -4.4221 -3.0078 -4.2875 3.0943 2.5905 3.902 4.428 4.662 3.2559 3.9791 3.3998 4.7465 4.5044 0.0781 0.5721 0.9192 0.6365 -1.118 0.665 0.7138 0.6245 1.5803 2.5749 3.9615 4.5067 4.6207 5.708 3.9106 4.4162 2.5264 1.4879 0.4811 0.3779 0.5113 -0.5574 -1.344 -1.2886 -1.943 -0.4439 0.1505 -1.0919 0.2435 -2.1727 -2.836 -2.8011 -1.5745 -1.2207 -1.8382 -2.1483 -1.5894 -2.6864 -2.894 -0.2065 0.4208 -0.7255 0.4551 -1.8765 -2.5224 -1.9322 -3.9163 46 H51 C52 H53 C54 H55 C56 H57 -2.2261 -0.2578 -0.3175 0.8874 1.7284 0.9615 1.8723 1.0306 0.1961 0.2416 -0.303 -0.6519 -0.3552 -0.746 -4.3935 -4.6994 -5.7884 -4.077 -4.6805 -2.6822 -2.2195 Referenced crystal structure Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 Atom X 0 -3.19011 3.739069 -1.80498 0.290699 1.892773 -3.13921 -3.19208 -4.04611 -4.36826 -4.828 -1.96018 -0.76442 -0.60189 -1.34952 0.691067 0.832807 1.784846 2.671121 1.531718 2.421194 4.216706 4.579689 4.92375 2.975911 2.83754 -3.42247 -2.65083 -3.51679 -2.7322 Y 0 0.391285 0.586127 0.058345 0.504917 0.098875 -0.11576 -1.00331 -0.11366 -1.0268 0.479081 0.364716 0.684129 1.107278 1.237237 1.33284 1.623214 1.144225 1.298864 0.720435 0.456133 0.352316 1.1867 -0.33914 -0.12624 0.477212 1.002641 1.026196 2.377153 2.527701 Z 0 -2.30224 -1.15101 -0.56396 -1.80672 0.033999 0.03572 0.488912 -1.21367 -1.416 -1.07854 -1.808 -2.60187 -3.91351 -4.48421 -4.35762 -5.25115 -3.52423 -3.82785 -2.22765 -1.08117 0.215446 0.606936 0.225216 1.008661 1.795248 1.049156 1.685321 0.405426 -0.16237 47 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 H51 C52 H53 C54 H55 C56 H57 -3.55317 -4.32956 -4.66672 -4.79961 -4.55288 -5.44606 3.01207 2.095747 3.96646 4.877269 3.937505 3.698779 3.334512 2.756423 3.185419 4.27182 -0.29431 -0.77225 -0.96417 -0.97178 -1.28891 -0.7129 -0.85184 -0.25172 -0.07943 -0.03815 0.28881 L1NiIIBr2 O N i-Pr O Npy NiII Br1 N Br2 i-Pr The geometry of this species was calculated using Orca 6.10 3.062143 2.42541 0.669481 1.353687 -0.20589 0.644783 -1.57152 -1.79351 -1.72378 -1.50802 -2.6485 -1.11598 -2.55423 -2.37629 -3.46931 -2.45009 -0.48258 -1.75205 -2.36946 -2.12464 -2.99803 -1.2409 -1.5001 0.020083 0.635799 0.398608 1.269501 1.105498 -0.14064 1.861657 2.549688 2.289767 1.26967 1.492914 1.826548 2.667563 2.379475 2.993617 3.388418 0.377717 -0.39401 0.694547 0.112442 1.794371 2.118002 1.421628 3.435517 3.638899 4.448828 5.350961 4.162243 4.864652 2.834179 2.639375 48 Calculated geometry Ni1 Br2 Br3 O4 O5 N6 N7 N8 C9 H10 C11 H12 H13 C14 C15 C16 H17 C18 H19 C20 H21 C22 C23 C24 H25 H26 C27 H28 C29 H30 C31 H32 H33 H34 C35 H36 H37 H38 C39 Atom X 0 0.438 -0.2351 3.1793 -3.8214 2.0256 -0.2929 -2.1421 3.4357 3.6011 4.1908 5.0048 4.5624 2.0215 0.7536 0.6032 1.4731 -0.6932 -0.8523 -1.7874 -2.8087 -1.5314 -2.5231 -4.485 -4.947 -5.2646 -3.3472 -3.328 3.8159 3.5519 5.3243 5.9101 5.6052 5.6275 3.0479 3.2606 3.3438 1.9646 -3.3931 Y 0 1.7433 -2.4253 0.798 0.7433 0.1116 0.7093 0.2706 0.0431 0.8852 0.2731 1.0011 -0.6656 0.5683 0.8872 1.3264 1.4677 1.5717 1.916 1.3745 1.5534 0.9359 0.6451 0.2273 -0.7295 0.9407 0.077 -0.9435 -1.252 -2.0844 -1.283 -1.2384 -2.2074 -0.4353 -1.4114 -0.5726 -2.3408 -1.4531 1.0665 Z 0 1.647 -0.2669 -2.5967 -1.5011 -0.7997 -1.8854 -0.0953 -0.3723 0.3207 -1.6979 -1.635 -2.1328 -1.9919 -2.6839 -3.9954 -4.6343 -4.4512 -5.473 -3.6065 -3.9381 -2.3119 -1.2536 -0.3142 -0.5848 -0.0267 0.7241 1.1298 0.3473 -0.3265 0.6011 -0.3277 1.1235 1.2347 1.6563 2.3359 2.1624 1.4913 1.8995 49 H40 C41 H42 H43 H44 C45 H46 H47 H48 -2.4559 -3.4209 -4.3428 -2.5597 -3.3797 -4.5636 -5.5306 -4.5581 -4.5152 0.9056 2.5229 2.7616 2.7605 3.1936 0.7358 0.8756 1.3934 -0.3043 2.4536 1.4422 0.89 0.8034 2.3114 2.8237 2.3161 3.7037 3.1766 Referenced crystal structure Ni1 Br2 Br3 O4 O5 N6 N7 N8 C9 H10 C11 H12 H13 C14 C15 C16 H17 C18 H19 C20 H21 C22 C23 C24 H25 H26 C27 H28 Atom X 0 0.4338 -0.2151 3.1741 -3.7978 1.9901 -0.2845 -2.1137 3.4139 3.5974 4.1648 4.9558 4.459 2.0093 0.7562 0.6243 1.3747 -0.6596 -0.7898 -1.7493 -2.6253 -1.5143 -2.4936 -4.4664 -4.9342 -5.1237 -3.3214 -3.377 Y 0 1.7393 -2.4003 0.7156 0.9811 0.0911 0.7453 0.2986 0.064 0.9023 0.1499 0.7396 -0.7463 0.5314 0.9243 1.4635 1.5704 1.8425 2.2288 1.6571 1.9121 1.0893 0.7773 0.4036 -0.4361 1.039 0.1298 -0.8168 Z 0 1.5924 -0.2258 -2.5904 -1.3866 -0.7638 -1.8246 -0.0481 -0.3245 0.1892 -1.661 -1.5854 -1.9595 -1.9637 -2.6363 -3.906 -4.4792 -4.309 -5.1671 -3.4593 -3.7233 -2.2204 -1.1671 -0.2136 -0.4523 0.166 0.7915 1.109 50 C29 H30 C31 H32 H33 H34 C35 H36 H37 H38 C39 H40 C41 H42 H43 H44 C45 H46 H47 H48 3.8087 3.6264 5.312 5.8091 5.574 5.5153 3.0099 3.0971 3.3549 2.0653 -3.3025 -2.4545 -3.2988 -4.1331 -2.539 -3.2229 -4.4611 -5.3087 -4.424 -4.3922 -1.1241 -1.9708 -1.0269 -1.1303 -1.7355 -0.153 -1.1368 -0.268 -1.8407 -1.3092 1.0672 0.8925 2.5379 2.7516 2.7136 3.0954 0.7526 0.8817 1.3513 -0.1769 0.5502 0.0501 0.8317 -0.0071 1.4568 1.2249 1.8525 2.2977 2.44 1.6547 1.9946 2.4956 1.5944 1.1275 1.0023 2.3967 2.9348 2.4616 3.7106 3.2361 4.2.2: Calculated structures for the catalytic cycle L1NiIIAr+ O N1 i-Pr Npy NiII O N2 i-Pr F Calculated geometry Ni1 O2 O3 Atom X 0 -3.2521 3.6689 Y 0 1.7194 0.4633 Z 0 1.4943 1.447 51 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 -1.8392 0.2167 1.9068 -3.1586 -3.1542 -4.084 -4.3962 -4.962 -2.0296 -0.8562 -0.7522 -1.6284 0.5227 0.6457 1.6426 2.6378 1.4329 2.3771 4.2192 4.5427 5.0856 3.0471 2.884 -3.4802 -2.6733 -3.466 -3.6551 -4.2457 -2.4942 -4.7997 -5.6509 -4.9933 -4.7812 3.1878 2.2369 4.3071 5.2904 4.3576 4.1422 3.3703 4.3015 2.5317 3.4229 0.5401 1.1334 -0.1922 0.2025 0.4222 1.188 2.0392 0.7226 1.3275 1.7281 2.5584 3.0499 2.7326 3.3755 2.0969 2.2262 1.2885 0.4895 -0.4931 -1.3709 -0.0226 -0.7918 -1.8733 -1.2882 -1.8269 -1.7093 -2.7878 -1.1953 -1.5066 -1.6354 -1.1203 -2.7146 -1.3582 -0.2091 -0.4393 -0.9245 -0.7392 -0.5689 -2.0113 1.307 1.6081 1.8177 1.6833 0.2275 1.5358 0.2394 -0.3333 -1.4079 0.417 -0.1985 0.8757 1.2294 2.0425 3.1521 3.5716 3.7024 4.574 3.1546 3.5766 2.0438 1.2263 0.4892 1.0598 0.0138 -0.4746 -0.5572 -0.1397 -0.6588 1.3281 1.4144 1.9108 1.8009 -0.8266 -0.3558 -0.7614 -1.8903 -1.89 -2.3931 -2.6443 -2.1857 -3.6823 -2.6665 -1.8881 -1.3844 -1.3933 -2.9187 52 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 -0.2123 0.1654 0.5913 0.0116 0.3002 -0.5223 -0.6711 -0.9071 -1.3216 -0.7514 -1.0612 -1.1102 -2.4615 -2.8909 -3.2954 -4.3473 -2.7589 -3.5523 -1.4278 -1.0443 -0.6169 0.4291 -1.5054 -1.4745 -0.5638 -2.5853 -2.5611 -3.7489 -4.8283 -3.831 -4.7645 -2.7036 -2.7754 (R) Radical addition Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 Atom X 0 -3.9826 2.3865 -1.8976 -0.7696 1.5667 -2.7227 -2.5071 -4.1616 -4.6412 -4.83 Y 0 0.3983 0.6221 -0.1002 0.7754 -0.0699 -0.5948 -1.6646 -0.398 -1.3395 0.1606 Z 0 -0.1745 -3.1551 0.4791 -1.5891 -1.1856 1.5939 1.7269 1.0438 0.7435 1.7097 53 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 -2.6853 -2.0922 -2.7004 -3.7812 -1.874 -2.3143 -0.4946 0.1542 0.0219 1.374 3.5283 4.2979 3.9 2.96 3.4526 -2.4034 -1.3116 -2.7607 -3.8517 -2.3373 -2.3688 -3.0769 -2.7603 -4.1764 -2.8176 3.0696 2.6356 4.5424 5.0432 4.6289 5.0982 2.2674 2.3415 2.6394 1.2004 0.6359 1.5966 2.0203 2.0616 2.8163 1.5536 2.0024 0.5916 0.4256 0.949 1.4637 1.6039 1.7703 2.1774 1.5256 1.7164 1.0027 0.5239 -0.0066 0.765 -0.795 -0.5326 -0.03 0.1213 0.0245 1.61 1.768 2.1299 2.1044 -0.6129 -1.6675 -0.5918 -0.1386 -2.0556 -2.2453 -2.4749 -2.3307 -3.5419 -1.8974 -2.8591 -3.936 -2.7066 -2.5866 -1.1501 -0.8771 0.1219 -1.8833 -1.6782 -3.1713 -4.1456 -3.4805 -0.4032 -1.6425 -2.7868 -2.8306 -3.8774 -4.7899 -3.8237 -4.6795 -2.638 -2.3184 -2.4895 -2.3671 -3.1568 -1.1407 -0.2962 2.9203 3.0434 2.9042 2.8939 2.0327 3.8064 4.084 4.1281 3.9911 5.0433 -0.9257 0.0671 -0.8783 -1.8507 -0.62 -0.1219 -1.9514 -1.7335 -2.979 -1.9302 1.3643 2.3449 2.4449 3.202 3.965 3.0652 3.8833 2.1077 54 H55 C56 H57 C58 C59 H60 C61 C62 Si63 H64 H65 C66 C67 C68 H69 H70 H71 C72 H73 H74 H75 H76 H77 H78 H79 C80 C81 H82 H83 H84 H85 H86 H87 0.2138 0.1356 -0.6126 0.4629 0.4562 -0.4725 1.7207 0.4113 0.0545 1.6618 2.5981 1.9502 0.2201 3.188 2.0444 1.0576 4.0746 3.4226 3.0857 4.3198 3.5592 2.5647 -0.0223 -0.4656 1.2483 1.2581 -1.7114 -1.8259 -2.4284 -1.9796 2.3046 1.0698 1.1355 -4.5027 -2.4598 -2.7134 2.0248 1.7415 2.4629 2.5928 1.4946 1.2179 2.524 2.0025 4.0688 2.8665 4.6527 4.1653 4.6539 4.0594 6.1265 4.5285 6.5164 6.2754 6.7454 2.7458 3.6167 3.2564 -0.0377 0.5673 -0.369 1.3006 0.3655 0.2323 -1.0488 -0.0785 2.0285 1.2648 0.5079 1.0082 2.3806 0.6418 0.3881 3.5896 5.3809 -0.7087 0.6995 0.7515 6.2762 0.0664 1.8474 0.465 0.3557 0.3961 -1.0276 -0.1114 1.4807 0.0828 7.3457 5.8498 6.1989 6.106 5.4938 4.9243 5.0899 6.5445 5.8892 5.7126 7.2015 55 (S) Radical addition Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 Atom X 0 -3.3573 1.2083 -1.3622 -1.1771 1.1466 -1.6159 -0.797 -2.9396 -2.8067 -3.7518 -2.3718 -2.33 -3.2267 -4.1655 -2.8751 -3.5577 -1.6504 -1.3564 -0.8084 0.5505 2.4807 2.4514 3.2797 2.52 Y 0 -1.3021 3.7909 -1.2076 1.2969 1.5579 -2.6563 -3.0994 -2.7019 -3.076 -3.2512 -0.5839 0.8829 1.7968 1.4614 3.1524 3.8965 3.5664 4.6166 2.5791 2.6609 3.4339 3.8282 3.9289 1.8826 Z 0 -1.7244 -0.0538 -0.7074 -0.77 0.1148 -0.8051 -1.3903 -1.6189 -2.6426 -1.1281 -1.2261 -1.2944 -1.8481 -2.2898 -1.8145 -2.2297 -1.2682 -1.2537 -0.7602 -0.21 0.5807 1.6054 0.0156 0.526 56 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 H60 C61 C62 Si63 H64 H65 C66 C67 C68 2.7012 -1.6447 -0.7223 -2.8399 -2.7138 -3.7856 -2.9523 -1.5696 -0.6653 -2.4472 -1.5478 3.5545 3.3895 4.9754 5.1173 5.2092 5.7136 3.3454 3.4878 2.337 4.072 1.2808 1.8523 1.5191 2.8697 3.3178 3.3142 4.292 2.7749 3.1501 1.7566 1.3426 -0.9971 -2.3554 -0.7658 -0.2362 -3.5444 -5.371 -0.4145 0.8448 -0.6368 -6.0353 0.1321 1.4672 -3.3596 -3.0352 -2.9604 -3.3589 -3.3706 -1.8707 -4.8775 -5.167 -5.2546 -5.3919 1.2729 0.1846 1.5558 1.1972 2.6338 1.0478 1.7231 2.8106 1.468 1.2259 -1.2934 -1.4503 -0.8439 -2.3862 -2.5157 -3.165 -4.0692 -3.0361 -3.6624 -2.0974 -1.997 0.2922 0.5364 -0.7434 1.3531 0.7682 0.9964 2.3437 1.1614 1.4064 -0.2803 2.4745 1.528 0.5664 1.0755 1.4356 2.4545 1.0438 1.5134 0.3708 -0.1885 -0.1826 1.3442 -0.4435 -0.3974 0.0531 1.0856 0.0325 -0.5868 -1.8917 -2.0101 -2.2545 -2.553 0.5055 1.7744 2.619 2.0016 2.9897 0.9375 1.1486 -0.3393 -1.1522 -0.5438 -1.5512 2.0674 1.8236 2.3393 2.8359 1.5896 1.433 2.3858 2.7725 4.3199 0.2181 5.1012 57 H69 H70 H71 C72 H73 H74 H75 H76 H77 H78 H79 C80 C81 H82 H83 H84 H85 H86 H87 -0.4656 -1.7218 1.2164 -0.2628 -0.0351 0.3055 -0.0753 -1.3357 -7.1317 -5.8023 -5.6042 -5.7332 -6.1287 -7.2246 -5.735 -5.9087 -6.8234 -5.3285 -5.2973 0.4152 1.598 2.2768 2.542 3.4586 3.3195 1.5804 2.7722 -0.187 -1.3011 -0.1565 2.7492 0.7217 0.8411 1.4481 -0.2926 2.915 2.9359 3.4914 4.7775 4.3958 5.0145 6.5765 4.6259 7.1123 7.0837 6.6911 0.1388 0.5628 -0.7867 0.8451 3.1374 3.0907 3.867 3.5082 0.8101 -0.1614 1.5338 (R)-NiIII Calculated geometry Ni1 O2 Atom X 0 -2.9084 Y 0 -1.9955 Z 0 -2.2555 58 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 3.6098 -1.9908 0.376 2.1245 -3.3867 -3.3877 -3.9724 -4.197 -4.8549 -1.8632 -0.5767 -0.3455 -1.1436 0.9257 1.1449 1.9124 2.908 1.5869 2.4713 4.2176 4.4749 5.1335 3.1336 2.6511 -4.1088 -3.5146 -4.1517 -4.7198 -3.1402 -4.635 -5.4998 -6.145 -5.9932 -5.448 3.6331 2.7461 4.6111 5.5314 4.9045 4.1678 4.231 3.5078 4.5342 0.7377 -0.7128 -0.7035 0.6502 -0.8718 -1.3526 -1.8416 -2.8343 -1.455 -1.3494 -1.3708 -1.9687 -2.5091 -1.8389 -2.2921 -1.1151 -0.9772 -0.5605 0.283 1.5427 2.5156 1.0325 1.6156 2.605 0.4783 1.0636 1.2613 0.7336 1.4477 2.2357 0.2731 -0.3121 1.2396 -0.2554 1.369 1.4574 2.4749 2.431 2.3694 3.4724 -0.0182 -0.8086 -0.139 -2.051 -0.6606 -1.8366 -0.3711 -0.223 0.7648 -1.2793 -0.8731 -1.8011 -1.7582 -2.4837 -3.7182 -4.2244 -4.2774 -5.2441 -3.6068 -4.025 -2.3735 -1.5413 -1.0048 -1.4353 -0.6818 0.097 0.0872 -0.0879 0.6305 -1.3951 -2.1757 -1.7752 -1.2411 0.5089 -0.164 0.6784 1.4718 1.5263 2.1719 1.9247 1.3222 2.9778 1.7934 1.7395 1.5082 2.7885 59 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 H60 C61 C62 Si63 H64 H65 C66 C67 C68 C69 C70 H71 H72 C73 H74 H75 H76 H77 H78 H79 H80 H81 H82 H83 H84 H85 H86 H87 5.127 0.3599 1.562 2.3439 1.8081 2.7485 0.8256 1.0504 -0.3874 -1.145 -0.607 -1.5692 -0.3112 -0.5227 0.6611 -1.4376 -0.5209 -0.47 -1.0791 -2.2738 -1.9534 -1.7242 -0.866 1.2718 -3.0813 -1.1207 -2.3079 -3.6119 -3.9015 -2.7245 -4.424 -2.8178 -4.0039 -0.9921 -0.0438 -1.7906 -1.7249 -2.7367 -1.4851 1.5816 1.9951 1.3189 -0.1807 -1.6853 -2.3585 -1.8898 -3.6451 -4.1603 -4.2706 -5.509 -3.6512 -4.1715 -2.3655 -1.9032 0.9666 1.8629 1.0851 0.5981 2.1377 3.0775 -0.179 0.1621 1.7953 4.457 1.942 3.7392 1.4204 2.2476 2.5703 2.6077 0.9618 0.6384 2.3095 3.0633 3.3892 2.5591 1.2406 1.368 5.0697 4.0553 5.1099 4.3316 2.9247 4.3874 1.1222 0.9088 0.6555 0.0593 1.1436 0.9438 1.8955 2.3743 2.1595 2.747 1.6598 1.8725 1.7565 0.6847 2.2452 2.6928 -0.5292 -2.1521 3.381 2.1303 3.4941 -1.9999 -3.5896 -2.3497 4.4508 4.0575 2.7941 5.246 3.8738 5.1409 5.9236 5.8562 4.5778 -4.4921 -3.7858 -3.4462 -2.914 -1.8541 -1.1481 -1.4771 -2.4979 -3.2378 60 (S)-NiIII Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 Atom X 0 -2.6921 4.0366 -1.899 0.6153 2.3222 -3.3509 -3.5454 -3.8824 -4.3724 -4.5481 -1.672 -0.2932 0.0631 -0.7037 1.4164 1.7349 2.3601 3.4224 1.9065 2.765 4.5474 4.6244 5.5415 Y 0 -1.4035 0.1419 -0.3356 -0.6625 0.1244 -0.3557 -0.9474 -1.1041 -2.0539 -0.5007 -0.9288 -1.0927 -1.5893 -1.9404 -1.5984 -1.972 -1.1121 -1.0858 -0.6576 -0.1197 0.8382 1.9025 0.4383 Z 0 -2.8685 -1.3203 -1.0637 -1.7917 0.1322 -0.8415 0.0642 -2.0911 -1.8514 -2.7191 -2.1679 -2.6672 -3.9161 -4.6045 -4.2529 -5.2259 -3.3485 -3.5843 -2.1138 -1.039 -0.1545 -0.4103 0.0622 61 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 C60 H61 C62 Si63 C64 C65 C66 H67 3.4938 3.2375 -3.9255 -3.4217 -3.6232 -4.0849 -2.5422 -4.0161 -5.4211 -5.9864 -5.8206 -5.6225 3.9498 4.2119 2.8594 2.6584 3.1853 1.9223 5.1937 6.0505 5.5083 4.9739 -0.2105 0.7467 1.6362 0.6194 1.3694 -0.4899 -0.6227 -1.4652 -2.3248 -1.3155 -2.0956 -0.7059 -0.4144 0.0414 -1.7685 -0.0034 0.5123 -0.3728 0.015 2.373 0.1138 0.5498 1.4613 1.0513 1.4396 2.0046 1.6725 2.0977 3.0065 0.9671 0.5966 1.9588 0.2947 -0.5447 -1.4239 -0.9494 -0.1334 -1.8213 -1.2088 -0.0936 0.1268 -0.879 0.8095 -1.7098 -2.7017 -2.4736 -3.9999 -4.7663 -4.3088 -5.5554 -3.363 -3.6389 -2.0723 -1.3466 0.9932 1.9262 1.0204 0.7421 2.2048 3.1423 4.7885 2.1815 3.3454 2.841 0.9353 1.4935 -0.6183 0.2806 -1.7703 -2.7123 -1.932 -1.5497 -0.3169 -1.1856 -0.0652 0.5294 1.9205 1.3059 2.9067 3.6155 3.4907 2.4041 2.6889 2.039 3.3895 3.2787 0.9012 0.6443 0.0557 1.1442 0.9443 1.9172 2.4091 2.1969 2.8092 1.6835 1.9179 1.6053 0.5878 2.9146 1.696 -0.553 -2.0936 -2.01 -3.623 -2.0355 -4.4984 62 H68 H69 H70 H71 H72 H73 H74 H75 H76 C77 H78 H79 C80 H81 C82 H83 H84 H85 H86 H87 0.6723 -1.0252 -0.0989 -1.4631 -0.1015 2.6974 2.8889 2.6971 1.0975 -0.5463 0.0048 -1.6139 0.1814 -0.5084 -0.4012 0.1508 1.2477 -0.3536 -1.4574 0.142 1.3177 1.8314 5.4085 4.6476 5.3358 3.7866 2.3847 4.0117 1.2539 2.0293 0.0145 1.8041 2.0277 3.039 3.0194 1.0102 2.251 4.0484 2.7949 2.9964 -3.7897 -3.5826 -2.8769 -2.0186 -1.0957 -1.0821 -2.1711 -2.849 2.7308 3.9026 3.3557 4.0615 5.244 3.4609 6.2444 5.667 5.0747 5.8575 6.4555 7.1994 (R) Reductive elimination Calculated geometry Ni1 Atom X 0 Y 0 Z 0 63 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 -3.2865 3.563 -2.0752 0.1636 2.3087 -3.4589 -3.4945 -4.2142 -4.4149 -5.1432 -2.1234 -0.9163 -0.8797 -1.7861 0.3426 0.4164 1.4673 2.4366 1.3265 2.4213 4.4812 5.0563 5.1587 3.5656 3.3254 -3.9626 -3.2178 -4.0292 -4.7367 -3.0467 -4.3742 -5.3048 -6.0871 -5.6399 -5.235 4.1774 4.2942 3.2786 3.2045 3.6788 2.265 5.5632 6.2759 -1.8565 -0.2975 -0.5482 -0.9882 0.3845 -0.3969 -0.627 -1.4849 -2.383 -1.1431 -1.3225 -1.6265 -2.4675 -2.9676 -2.6378 -3.2905 -1.9612 -2.0567 -1.1397 -0.3254 0.4562 1.1269 -0.2588 1.1708 2.1855 1.0411 1.6849 1.4338 0.8041 1.3592 2.4711 1.2339 0.5991 2.2764 0.9869 1.3028 0.2832 2.1149 3.1548 2.1308 1.7079 1.9465 1.341 -1.7734 -2.5133 -0.4122 -1.7592 -0.7704 0.0725 1.1444 -0.721 -0.1241 -1.1885 -1.4256 -2.2145 -3.3209 -3.6579 -3.9696 -4.8393 -3.5037 -3.9892 -2.3868 -1.8237 -1.6938 -2.3388 -1.2035 -0.6862 -1.0465 -0.128 0.3663 -1.602 -2.1614 -2.0881 -1.7062 0.5753 0.1318 0.4892 1.6445 0.7085 1.1129 1.6327 1.2807 2.6555 1.6658 0.6181 0.0418 64 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 H60 C61 C62 Si63 H64 H65 C66 C67 C68 C69 C70 H71 H72 C73 H74 H75 H76 H77 H78 H79 H80 H81 H82 H83 H84 H85 H86 H87 5.9849 5.4985 0.3922 1.7388 2.4999 2.1329 3.1809 1.1574 1.5258 -0.1898 -0.9305 -0.5644 -1.6246 -0.0724 -0.2383 0.8878 -1.2208 -0.2916 -0.2519 -0.9488 -2.1125 -1.56 -0.0925 1.2399 -1.8259 -2.6803 -0.6579 -1.855 -3.0493 -3.5677 -2.3799 -3.8562 -2.1855 -3.3883 1.292 1.1762 2.1744 -0.1115 0.8584 -0.9111 -2.7159 -1.9048 -1.826 2.0835 2.9389 -1.4014 -1.709 -0.9409 -2.9855 -3.23 -3.9559 -5.1887 -3.6801 -4.4613 -2.3975 -2.1858 0.5125 1.6464 0.5618 0.2368 2.2901 3.5293 -0.6157 -0.0621 1.4467 2.5534 4.6323 4.5402 1.1579 1.776 2.2894 2.3672 0.8069 0.3205 2.1325 2.7204 3.2052 5.3896 5.1557 4.0551 3.2237 2.0012 1.827 3.9085 5.0793 5.2829 1.623 0.1458 1.3643 1.5976 1.4709 1.995 2.1716 2.1805 2.5685 1.9934 2.1675 1.593 1.4656 2.0347 1.1572 2.5537 2.9932 0.0996 -1.2979 3.6295 2.4302 3.8619 -2.8896 -1.0349 -1.2401 4.8571 4.4041 3.2156 5.7086 4.3046 5.5077 6.4166 6.2916 5.0811 -1.8319 -0.0699 -1.0521 -3.7614 -2.9019 -2.994 -1.3548 -0.2848 -2.0522 65 (S) Reductive elimination Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 Atom X 0 -3.51 1.3989 -1.9363 -0.7756 1.3835 -2.8217 -2.2212 -3.7094 -3.3801 -4.7789 -2.4385 -1.8643 -2.3913 -3.2804 -1.754 -2.1381 -0.6399 -0.1395 -0.181 0.9296 2.2215 Y 0 -1.568 3.4765 -1.0229 0.7024 1.6963 -1.9485 -2.7494 -2.5068 -3.4937 -2.539 -0.8616 0.123 0.4888 -0.0052 1.5144 1.8325 2.1481 2.9716 1.6973 2.2762 3.8844 Z 0 -1.6331 -1.9259 -0.1326 -1.7323 -0.5574 0.5911 1.0432 -0.5413 -0.8899 -0.3095 -1.2949 -2.2349 -3.4689 -3.8574 -4.1693 -5.1385 -3.6187 -4.1254 -2.3844 -1.5996 -0.8017 66 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 H60 C61 C62 Si63 H64 H65 1.6629 3.145 2.4212 2.2 -3.5721 -2.7888 -4.4899 -4.985 -5.2845 -3.9352 -4.3312 -5.1272 -4.8075 -3.6609 3.8277 3.7639 4.8336 4.9335 5.828 4.5325 4.2761 4.4583 3.5359 5.2164 1.0761 0.4825 -0.4461 1.0703 0.6123 2.2749 2.8522 2.9026 3.8531 2.2997 2.8044 0.869 0.209 0.2591 2.3159 -0.4251 -1.3293 2.3578 2.9629 4.6477 4.3224 2.5821 2.7411 -1.2183 -0.7489 -0.1154 0.3974 -0.5182 0.6418 -2.2194 -2.7238 -1.7099 -2.9929 1.9715 0.9887 2.811 3.8213 2.345 2.9149 1.7625 2.72 1.2031 1.1951 -1.6277 -2.876 -3.1423 -3.8203 -4.7952 -3.5086 -4.4155 -2.288 -2.0765 -1.3605 -0.4162 -1.1128 0.0881 -1.9917 -1.2706 1.1507 2.7705 -0.9277 -0.5839 -0.2449 -1.1933 0.0028 1.0663 1.719 2.3353 1.1955 2.0311 0.5501 0.6246 2.5881 2.0194 3.4368 2.9893 -0.1089 0.3818 0.6768 0.2519 0.652 1.7289 -1.5548 -2.0642 -2.144 -1.5822 -0.4196 -0.6438 -0.141 -1.484 -1.6544 -2.0996 -2.9055 -1.8928 -2.3839 -1.0447 -0.866 1.5626 2.021 1.7967 2.0314 1.9896 2.1954 3.0771 1.4688 67 C66 C67 C68 C69 C70 H71 H72 C73 H74 H75 H76 H77 H78 H79 H80 H81 H82 H83 H84 H85 H86 H87 2.8582 -2.7233 -1.9677 -0.11 4.2988 2.2149 2.8025 4.8473 4.932 4.361 4.8229 5.8873 4.2514 -2.6279 -1.1344 -2.534 -3.2772 -3.4305 -2.3298 0.3267 0.7082 -0.6209 -2.6942 2.5064 3.2783 4.0358 -2.7888 -3.3491 -3.0826 -4.2106 -2.1321 -2.3873 -4.6215 -4.252 -4.8797 4.1537 3.5511 2.4646 3.4452 1.7466 2.1806 3.7106 4.2083 4.9961 1.968 3.4168 0.5066 2.8466 2.4618 2.5795 0.9413 2.4305 1.8424 3.4868 1.41 2.7831 3.0694 0.5939 -0.1568 0.0315 3.5683 3.059 4.3907 3.802 2.1331 3.0142 (R) Product-Catalyst Complex Calculated geometry Ni1 Atom X 0 Y 0 Z 0 68 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 -3.0909 3.6691 -2.0044 0.2798 2.1855 -3.3582 -3.2923 -4.0802 -4.3582 -4.96 -1.9841 -0.731 -0.5634 -1.4058 0.7159 0.8912 1.7714 2.7793 1.4967 2.4715 4.3152 4.3718 5.327 3.4019 3.1313 -3.9746 -3.2606 -4.1006 -4.844 -3.1417 -4.426 -5.3035 -6.0548 -5.7099 -5.1837 4.045 4.3656 3.0675 2.7328 3.5451 2.1757 5.2758 6.0319 -2.7077 -0.9892 -0.8068 -1.6776 0.0936 -0.5674 -0.3903 -1.9084 -2.4513 -1.8138 -1.9761 -2.5292 -3.7791 -4.4616 -4.1213 -5.0942 -3.2204 -3.4584 -1.9978 -0.9162 0.2754 0.8407 0.0597 0.9338 1.9579 0.6845 1.4916 0.5766 -0.179 0.3118 1.5361 1.0307 0.2441 1.9669 1.156 0.9763 -0.0549 1.4345 2.4644 1.4094 0.8035 1.884 1.5687 -0.6976 -1.8499 -0.2144 -1.1303 -0.5539 0.2911 1.3739 0.0065 0.9171 -0.6404 -0.7196 -1.2788 -1.8653 -1.9644 -2.3047 -2.7637 -2.1565 -2.4923 -1.5505 -1.2837 -1.5647 -2.5034 -1.2062 -0.5047 -0.7998 -0.3466 -0.1214 -1.8639 -2.1592 -2.3317 -2.2888 0.3201 0.1502 -0.0867 1.406 0.8912 1.1227 1.9662 1.7781 2.9552 1.9966 0.8769 0.1452 69 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 H60 C61 C62 Si63 H64 H65 C66 C67 C68 C69 C70 H71 H72 C73 H74 H75 H76 H77 H78 H79 H80 H81 H82 H83 H84 H85 H86 H87 5.7563 4.9854 -0.1391 1.1405 1.9869 1.359 2.3514 0.2736 0.4619 -1.0022 -1.8268 -1.1985 -2.2041 -0.3376 -0.3856 0.5713 -1.526 -0.451 -0.5976 -1.3739 -2.4585 -1.6882 -0.7285 0.9389 -2.1195 -2.7783 -1.9241 -0.7281 -2.8707 -2.5965 -3.7456 -3.6683 -3.0788 -1.9261 0.8443 1.0789 1.8394 -0.7969 0.1585 -1.6169 -3.0358 -2.0274 -2.2351 1.8917 2.9187 -1.6017 -2.0104 -1.3357 -3.2624 -3.5806 -4.111 -5.3049 -3.759 -4.4594 -2.5017 -2.2273 -0.1802 0.7789 0.0811 -0.0168 1.7267 3.2839 -0.7437 -0.3092 1.4016 2.7776 4.319 4.2245 2.2194 1.3427 1.9408 3.6493 2.2268 1.7091 4.2122 3.6704 4.1905 5.2724 4.5445 3.8077 3.6693 2.2031 2.1575 3.6265 4.5327 5.1318 1.8646 0.6383 2.5451 2.1457 2.2758 1.5769 1.2569 1.4105 0.8222 1.8277 1.6943 2.3978 2.7144 3.0704 1.9375 3.6368 4.0326 1.1457 0.1212 4.8429 3.5286 4.5967 -1.6795 0.3992 0.6789 3.9035 5.6702 4.534 4.4206 2.8188 4.0443 3.9157 5.501 4.2577 -0.1426 1.4664 0.0324 -2.3204 -1.9872 -1.8605 0.5761 1.7298 0.0666 70 (S) Product-Catalyst Complex Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 Atom X 0 -2.7444 3.7373 -1.8302 0.4732 2.0134 -3.2272 -3.2507 -3.8021 -3.997 -4.6997 -1.7009 -0.4135 -0.1007 -0.8392 1.1918 1.4795 2.1179 3.1298 1.7015 2.4998 4.1495 Y 0 -2.8414 -0.0322 -1.0818 -1.3525 0.5673 -1.0603 -1.1109 -2.3589 -3.137 -2.208 -2.0554 -2.2837 -3.3163 -4.0757 -3.3425 -4.1365 -2.3564 -2.3538 -1.369 -0.2328 1.2367 Z 0 -1.3494 -1.8979 -0.3032 -1.4805 -0.5936 0.1383 1.2353 -0.477 0.2696 -1.0874 -1.1167 -1.8124 -2.6902 -2.9418 -3.2191 -3.9084 -2.871 -3.2729 -1.9823 -1.4637 -1.3208 71 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 C60 C61 Si62 C63 C64 C65 4.1463 5.1676 3.0809 2.6922 -3.9044 -3.2903 -3.8949 -4.5023 -2.8751 -4.315 -5.3124 -5.9733 -5.7629 -5.3024 3.5373 2.6147 4.4542 5.3892 4.7256 3.9686 4.1884 3.543 4.3958 5.1479 -0.2669 0.7369 1.668 0.5634 1.3352 -0.636 -0.8268 -1.6406 -2.5583 -1.4438 -2.2307 -0.1101 -0.2868 1.222 -0.4753 -0.7711 -0.7233 0.5898 -2.4449 1.9814 1.1217 1.5171 2.5389 0.2499 1.0452 0.4508 -0.3083 0.4085 1.433 0.348 -0.4292 1.3215 0.2366 1.3095 1.3552 2.4458 2.4601 2.3274 3.4249 -0.0543 -0.8778 -0.2112 -0.1371 -2.0485 -2.5499 -1.9985 -3.7412 -4.1315 -4.4261 -5.5541 -3.978 -4.5578 -2.7859 -2.4178 -0.6943 0.3983 -0.5429 1.4505 3.1788 3.1196 4.2668 3.7479 -2.1264 -0.9349 -0.2417 -0.3425 -0.2934 0.1574 -1.8068 -2.3227 -2.2149 -2.0635 0.2887 -0.1248 0.051 1.3825 1.2126 1.8128 1.6603 1.0796 2.7184 1.5428 1.4336 1.098 2.5006 0.9021 2.3959 1.5589 1.4322 0.8603 0.196 1.0013 0.2965 1.8477 1.9504 2.5447 3.2057 3.0728 2.0857 3.8296 1.4646 0.8203 -1.0518 1.5102 1.4412 72 H66 H67 H68 H69 H70 H71 H72 H73 H74 H75 H76 C77 H78 C79 H80 H81 C82 H83 H84 H85 H86 H87 0.4534 0.5743 1.5817 -0.8726 0.2446 -1.5152 -3.2543 -2.476 -2.6437 -0.9285 2.0543 1.366 1.2985 2.71 1.245 0.5472 2.8748 2.8287 3.518 3.8483 2.8023 2.0926 5.3065 4.2558 3.9299 4.1251 2.7366 2.4643 3.1032 3.7423 4.7747 -0.5857 -0.6559 0.7824 -1.3816 0.9279 1.6135 0.888 2.2747 0.1116 0.7918 2.3556 3.1021 2.4297 1.1761 2.61 1.1792 -1.4722 -1.4072 -1.4428 1.0704 2.5406 1.0986 3.8016 3.1211 4.5683 4.5382 5.2762 3.8549 5.2999 5.9704 6.0073 4.5388 6.4738 5.2481 6.7287 73 4.2.3 Transition state structures for radical addition L1 + E2 TMS Br O N Me O N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 Atom X 0 -3.2327 1.5213 -1.3986 -1.0189 1.3097 -1.6991 -0.8629 -2.9708 -2.8293 -3.8571 -2.2769 -2.1273 -2.8939 -3.8 -2.4418 -3.0166 -1.242 Y 0 -0.9615 3.7219 -1.0943 1.4173 1.5007 -2.5043 -2.8923 -2.3939 -2.7664 -2.8632 -0.369 1.1052 2.0877 1.8305 3.4078 4.2074 3.7117 Z 0 -2.2176 -0.0076 -0.943 -0.8488 0.1364 -1.2461 -1.8438 -2.1251 -3.1448 -1.6845 -1.5369 -1.511 -2.1259 -2.6723 -2.0308 -2.4981 -1.3798 74 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 C60 H61 -0.8528 -0.5438 0.8021 2.826 3.0693 3.5531 2.6556 2.6322 -1.8184 -0.88 -2.9792 -2.9317 -3.9544 -2.9546 -1.8871 -1.0129 -2.7908 -1.9188 3.7296 3.491 5.1048 5.4205 5.8641 5.11 3.7002 2.7222 4.4594 3.9154 1.1497 1.6474 1.2887 2.6318 3.0256 3.1226 4.076 2.6566 3.0669 1.6689 1.317 -1.1412 -0.272 -2.5303 -1.064 4.7279 2.6574 2.6336 3.265 3.8186 3.5167 1.7409 1.4994 -3.3833 -3.2236 -2.9938 -3.5653 -3.2082 -1.9285 -4.8544 -5.1448 -5.0644 -5.5004 0.8671 -0.1662 1.2068 2.2257 0.5152 1.1315 0.9481 0.6432 0.2801 1.9642 -1.3755 -1.5577 -0.9389 -2.511 -2.6552 -3.2848 -4.2014 -3.1408 -3.7669 -2.1854 -2.0691 0.248 1.0814 0.7775 -0.8204 -1.3408 -0.8027 -0.1854 0.4568 1.3684 -0.3245 0.67 1.742 0.0056 0.5579 0.9156 1.8523 0.454 1.1757 -0.4023 -1.0024 -0.9953 0.4853 0.0051 0.2925 0.5788 0.3068 0.1894 1.6758 -1.5184 -1.9169 -1.9477 -1.883 0.5963 1.8914 2.7155 2.1662 3.1733 1.1237 1.3796 -0.1757 -0.9693 -0.4252 -1.4537 1.9958 2.7303 1.7373 2.2147 75 C62 Si63 C64 C65 C66 H67 H68 H69 H70 H71 H72 H73 H74 H75 H76 H77 H78 0.4424 1.4129 1.134 0.7641 3.2292 1.7502 1.3869 0.0791 -0.31 0.9131 1.2941 3.6878 3.7845 3.3636 -3.1231 -2.5154 -3.0683 1.8497 3.0255 4.7521 2.8833 2.5524 5.4865 4.8101 5.0432 3.115 1.8665 3.586 2.732 3.149 1.49 0.7243 1.828 0.188 3.3708 4.4311 3.7514 6.184 4.3817 4.2915 2.6832 3.8636 6.2269 6.5759 6.8449 3.3994 5.1212 4.6329 2.6651 1.4194 0.9858 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 Atom X 0 -3.3292 1.5719 -1.4408 -1.0289 1.3087 -1.7923 Y 0 -0.7882 3.6995 -1.0148 1.4824 1.4819 -2.4039 Z 0 -2.1338 0.1488 -0.9579 -0.7236 0.246 -1.2971 76 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 -0.9889 -3.0894 -2.9875 -3.9689 -2.3339 -2.1565 -2.909 -3.8269 -2.4305 -2.9961 -1.2169 -0.808 -0.5304 0.8236 2.8163 2.8705 3.6411 2.6981 2.8111 -1.9004 -0.9547 -3.0515 -2.9684 -4.0285 -3.0565 -1.9793 -1.1089 -2.8863 -2.0147 3.6887 3.4379 5.1191 5.4426 5.8167 5.2203 3.5343 2.5188 4.2343 3.752 1.1673 1.7375 1.4279 2.7247 -2.799 -2.2267 -2.5456 -2.7045 -0.2457 1.221 2.2425 2.025 3.5487 4.3777 3.8023 4.8084 2.7101 2.6361 3.2155 3.612 3.6209 1.6717 1.2449 -3.3123 -3.167 -2.9371 -3.4904 -3.192 -1.8657 -4.7737 -5.0579 -4.963 -5.4386 0.9604 -0.108 1.139 2.1898 0.5525 0.8031 1.3923 1.1994 0.8353 2.4629 -1.4337 -1.7954 -1.3082 -2.7817 -1.9338 -2.1262 -3.1686 -1.6816 -1.4671 -1.3743 -1.9409 -2.4849 -1.799 -2.2245 -1.1526 -1.0752 -0.6353 -0.0408 0.7375 1.7572 0.1419 0.6874 1.6929 -0.0654 0.4789 0.864 1.8094 0.4267 1.1003 -0.5044 -1.1131 -1.0996 0.3691 -0.2496 -0.1821 0.256 0.2043 -0.357 1.298 -1.7057 -2.0803 -2.3431 -1.8418 0.3854 1.6099 2.5356 1.6924 77 H51 C52 F53 C54 H55 C56 H57 C58 C59 H60 C61 C62 Si63 H64 H65 H66 C67 C68 C69 H70 H71 H72 H73 H74 H75 H76 H77 H78 3.1732 3.1423 4.0962 2.6009 2.953 1.6142 1.2016 -0.9637 -2.2926 -0.8387 -0.13 -3.446 -5.2437 -0.462 -0.2301 0.9316 -5.9034 -6.1244 -5.4124 -6.9772 -5.3864 -5.7774 -6.0007 -5.7281 -7.2014 -4.9104 -6.4753 -4.9772 -3.0655 -3.4087 -4.3566 -3.087 -3.6022 -2.1007 -1.8441 0.0878 0.4773 -0.9847 1.0078 0.8207 1.211 0.9472 2.0544 0.7367 0.0848 0.8759 3.0165 0.2708 0.2428 -0.9711 -0.1745 1.5133 1.0796 3.2314 3.2801 3.6688 2.6454 0.5271 0.598 -0.7099 -1.6046 -0.7665 -1.746 2.0777 1.8036 2.2508 2.9338 1.5542 1.3017 3.9834 2.6185 2.9114 -0.0453 2.9232 0.8226 -0.1992 -1.0014 0.2368 3.2248 3.727 2.823 -0.1308 0.7135 1.5938 78 L2 + E1 TMS Br n-Bu O O N N N Me Me (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 Atom X 0 -3.0962 3.5501 -1.8727 0.2759 1.7933 -3.1849 -3.5619 -4.0435 -4.8023 -4.5091 -1.9489 -0.7399 -0.5824 -1.4159 0.6805 0.8449 Y 0 1.9448 -0.3983 0.6117 0.9133 -0.7264 0.6393 -0.3893 1.4685 0.8759 2.347 1.3679 1.5675 2.2591 2.7948 2.2238 2.7562 Z 0 -1.6915 -1.8485 -0.3741 -1.6902 -0.5024 0.2972 0.3625 -0.6898 -1.213 -0.2296 -1.4102 -2.2412 -3.4364 -3.8877 -4.0361 -4.973 79 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 C31 C32 H33 C34 H35 C36 F37 C38 H39 C40 H41 C42 C43 H44 C45 C46 Si47 H48 H49 C50 C51 C52 H53 H54 H55 H56 H57 H58 C59 C60 1.7262 2.7027 1.4657 2.3082 3.9654 4.9323 4.079 2.8181 3.1144 -3.0825 -2.4046 2.3224 1.5073 -0.2906 0.4913 1.2789 0.3091 0.9177 -0.6684 -0.8462 -1.4673 -2.2242 -1.2706 -1.897 0.5735 1.9628 -0.0333 0.1032 3.1857 5.034 -0.9474 0.6917 0.2098 5.4752 -0.2994 -0.3634 0.2768 -1.3428 6.5665 5.0208 5.1221 5.7721 5.5883 1.4886 1.4196 0.8259 -0.1199 -1.4861 -1.2165 -2.3822 -1.6213 -1.2102 1.2323 0.6308 -3.0473 -3.0914 -1.0791 -1.068 -0.3225 -2.0135 -2.0107 -2.9858 -3.9064 -3.0356 -3.8157 -2.0756 -2.1276 1.9096 1.7337 1.5864 3.1544 1.6328 1.6457 3.0462 3.3106 4.4035 3.0602 5.658 4.2403 5.8078 5.4935 3.1223 2.9171 4.0196 1.9185 0.0139 -3.4685 -3.9451 -2.275 -1.5089 -0.9715 -0.5363 -1.595 0.0571 1.0331 1.6934 2.3115 0.2271 0.9586 1.5249 2.6871 2.8158 3.6991 4.6045 3.5355 4.5028 2.4022 2.3095 1.4061 0.512 1.2292 1.3665 2.0786 0.5156 1.4543 1.6382 0.2156 -0.4009 1.3981 2.7868 0.6939 2.3255 -0.234 0.3772 2.9154 3.778 2.3814 -0.0649 2.3802 80 H61 H62 H63 H64 H65 H66 C67 H68 H69 H70 H71 H72 H73 H74 H75 5.3938 5.0751 6.6708 5.4891 5.4214 6.8706 -0.2156 1.2586 -0.5859 -0.8133 0.8218 -2.7065 -4.0723 3.1429 1.9634 -0.8392 -0.1735 0.0441 2.9093 1.1655 1.8705 6.9079 4.5453 7.7951 6.7943 7.1097 2.2638 1.2406 -3.6845 -3.4466 1.7155 3.3348 2.5764 -0.4499 -0.7845 -0.0219 1.5619 1.7045 1.0295 2.4786 1.8676 1.6547 2.1687 0.5839 -0.7319 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 Atom X 0 -3.0962 3.5501 -1.8727 0.2759 1.7933 -3.1849 -3.5619 -4.0435 -4.8023 Y 0 1.9448 -0.3983 0.6117 0.9133 -0.7264 0.6393 -0.3893 1.4685 0.8759 Z 0 -1.6915 -1.8485 -0.3741 -1.6902 -0.5024 0.2972 0.3625 -0.6898 -1.213 81 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 C31 C32 H33 C34 H35 C36 F37 C38 H39 C40 H41 C42 C43 H44 C45 C46 Si47 H48 H49 C50 C51 C52 H53 -4.5091 -1.9489 -0.7399 -0.5824 -1.4159 0.6805 0.8449 1.7262 2.7027 1.4657 2.3082 3.9654 4.9323 4.079 2.8181 3.1144 -3.0825 -2.4046 2.3224 1.5073 -0.2906 0.4913 1.2789 0.3091 0.9177 -0.6684 -0.8462 -1.4673 -2.2242 -1.2706 -1.897 0.5735 1.9628 -0.0333 0.1032 3.1857 5.034 -0.9474 0.6917 0.2098 5.4752 -0.2994 -0.3634 2.347 1.3679 1.5675 2.2591 2.7948 2.2238 2.7562 1.4886 1.4196 0.8259 -0.1199 -1.4861 -1.2165 -2.3822 -1.6213 -1.2102 1.2323 0.6308 -3.0473 -3.0914 -1.0791 -1.068 -0.3225 -2.0135 -2.0107 -2.9858 -3.9064 -3.0356 -3.8157 -2.0756 -2.1276 1.9096 1.7337 1.5864 3.1544 1.6328 1.6457 3.0462 3.3106 4.4035 3.0602 5.658 4.2403 -0.2296 -1.4102 -2.2412 -3.4364 -3.8877 -4.0361 -4.973 -3.4685 -3.9451 -2.275 -1.5089 -0.9715 -0.5363 -1.595 0.0571 1.0331 1.6934 2.3115 0.2271 0.9586 1.5249 2.6871 2.8158 3.6991 4.6045 3.5355 4.5028 2.4022 2.3095 1.4061 0.512 1.2292 1.3665 2.0786 0.5156 1.4543 1.6382 0.2156 -0.4009 1.3981 2.7868 0.6939 2.3255 82 H54 H55 H56 H57 H58 C59 C60 H61 H62 H63 H64 H65 H66 C67 H68 H69 H70 H71 H72 H73 H74 H75 0.2768 -1.3428 6.5665 5.0208 5.1221 5.7721 5.5883 5.3938 5.0751 6.6708 5.4891 5.4214 6.8706 -0.2156 1.2586 -0.5859 -0.8133 0.8218 -2.7065 -4.0723 3.1429 1.9634 5.8078 5.4935 3.1223 2.9171 4.0196 1.9185 0.0139 -0.8392 -0.1735 0.0441 2.9093 1.1655 1.8705 6.9079 4.5453 7.7951 6.7943 7.1097 2.2638 1.2406 -3.6845 -3.4466 -0.234 0.3772 2.9154 3.778 2.3814 -0.0649 2.3802 1.7155 3.3348 2.5764 -0.4499 -0.7845 -0.0219 1.5619 1.7045 1.0295 2.4786 1.8676 1.6547 2.1687 0.5839 -0.7319 83 L2 + E2 TMS Br O N Me O N N Me Me (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 Atom X 0 -3.7876 3.059 -2.0089 -0.3348 1.7717 -3.1215 -3.1969 -4.347 -5.056 -4.8763 -2.4935 -1.5792 -1.8642 -2.885 -0.7922 Y 0 0.9755 0.437 0.0882 0.8718 -0.2728 -0.2328 -1.3258 0.3442 -0.4203 1.1187 0.7454 1.2113 1.8526 2.1295 2.11 Z 0 -0.9899 -2.5762 0.0398 -1.7029 -0.8895 0.9523 1.0256 0.1997 -0.1358 0.7667 -0.9517 -2.0191 -3.2186 -3.4772 -4.079 84 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 C31 C32 H33 C34 H35 C36 F37 C38 H39 C40 H41 C42 C43 H44 C45 C46 Si47 H48 H49 C50 H51 H52 H53 C54 C55 H56 H57 H58 H59 -0.9741 0.5047 1.3418 0.6849 1.8867 3.9229 4.8495 4.1435 3.0909 3.4604 -2.9041 -1.9855 3.041 2.4312 0.3429 1.3266 1.8948 1.6276 2.3942 0.9337 1.221 -0.0479 -0.57 -0.336 -1.1037 0.2764 1.6571 -0.004 -0.6594 2.8493 4.6243 -1.7069 -0.4043 4.9026 5.9413 4.7171 4.2338 4.8977 5.731 5.632 5.4974 6.7838 4.2934 2.6138 1.6997 1.856 1.0588 0.3985 -0.4565 0.0813 -1.3206 -0.8388 -0.3177 0.3531 -0.0506 -2.3349 -2.5566 -1.0466 -0.7788 0.1531 -1.6937 -1.4906 -2.8956 -3.7857 -3.2047 -4.1605 -2.2711 -2.5263 2.0332 2.2374 1.5974 3.0773 2.4655 2.9673 2.7572 3.3546 4.5222 4.8687 4.3354 5.3306 3.3077 1.5888 0.6633 1.3554 1.9053 4.1695 -5.0283 -3.7542 -4.4329 -2.5342 -1.9767 -1.8144 -1.5923 -2.4541 -0.5676 0.3276 2.3375 2.7806 -0.3086 0.5749 1.536 2.4963 2.4599 3.508 4.2571 3.5488 4.5183 2.6181 2.6815 1.619 0.8841 1.1008 0.9053 2.0624 0.5466 0.7089 0.487 0.5854 -0.4846 1.4969 1.3849 2.5646 1.1673 -1.3377 1.1164 0.5324 2.1656 1.0653 -1.6577 85 H60 H61 H62 H63 H64 H65 H66 C67 H68 H69 H70 H71 H72 H73 H74 H75 4.6137 5.9551 -2.8255 -3.7488 4.0567 2.6184 -0.585 -0.0739 1.4003 -0.4442 -0.6716 0.9635 -2.5648 -3.9306 3.2846 2.1051 2.4493 3.5423 1.4476 0.0924 -2.7142 -2.8618 3.9935 6.5365 4.1739 7.4237 6.4229 6.7383 1.8924 0.8692 -4.0559 -3.818 -1.962 -1.532 2.2911 2.989 -0.1322 -1.1755 1.1549 1.7605 1.9031 1.2281 2.6772 2.0662 1.8533 2.3673 0.7825 -0.5333 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 Atom X 0 -3.4191 1.3615 -1.4021 -1.1154 1.2235 Y 0 -1.1161 3.7802 -1.1586 1.3647 1.5626 Z 0 -1.8018 -0.1309 -0.8341 -0.8168 0.1219 86 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 C31 C32 H33 C34 H35 C36 F37 C38 H39 C40 H41 C42 C43 H44 C45 C46 Si47 H48 H49 -1.8088 -1.0617 -3.1509 -3.1018 -3.99 -2.3632 -2.2356 -3.0416 -3.9519 -2.6263 -3.2347 -1.4218 -1.0642 -0.6782 0.6773 2.629 2.661 3.4345 2.5972 2.7214 -1.918 -0.9449 3.6205 3.5092 1.2337 1.8842 1.6175 2.8959 3.4043 3.2598 4.2343 2.6452 2.9592 1.6338 1.1601 -1.0218 -2.3955 -0.6968 -0.3711 -3.5904 -5.434 -0.635 0.7209 -2.5751 -3.1518 -2.535 -3.0017 -2.9524 -0.4778 0.9935 1.9231 1.6128 3.2574 4.0167 3.6263 4.6546 2.6194 2.665 3.4115 3.8918 3.802 1.8645 1.5175 -3.1195 -3.0622 1.1832 0.093 -1.3328 -1.4407 -0.7822 -2.3803 -2.467 -3.2193 -4.1276 -3.1481 -3.823 -2.2032 -2.1485 0.1496 0.249 -0.8493 1.3082 0.3532 0.4927 2.269 1.2141 -0.8304 -1.3907 -1.6015 -2.5915 -1.0339 -1.346 -1.4248 -2.0715 -2.5819 -2.0539 -2.5452 -1.4454 -1.4591 -0.8426 -0.2494 0.4916 1.4758 -0.1403 0.558 1.5923 0.5848 1.0885 -0.338 -0.2879 0.5221 1.7567 2.5856 1.9715 2.9327 0.9275 1.1255 -0.3147 -1.1121 -0.5038 -1.4873 2.0719 1.7676 2.3711 2.7829 1.498 1.3126 2.3212 2.7984 87 C50 H51 H52 H53 C54 C55 H56 H57 H58 H59 H60 H61 H62 H63 H64 H65 H66 C67 H68 H69 H70 H71 H72 H73 H74 H75 -6.0591 -7.1575 -5.7679 -5.6555 -5.8286 -6.1602 -7.2568 -5.7769 -5.9075 -6.918 -5.4569 -5.38 -2.6525 -2.2333 4.6359 3.4937 -0.7121 -1.2946 0.1796 -1.6649 -1.8923 -0.2572 -3.7855 -5.1513 2.0639 0.8844 -0.9788 -0.952 -1.9246 -0.9706 2.0996 0.4984 0.58 1.347 -0.4291 2.2523 2.0928 2.9574 -2.5446 -4.171 1.4459 1.5053 1.3446 5.964 3.6014 6.8512 5.8504 6.1658 1.3199 0.2967 -4.6284 -4.3905 0.3343 0.2725 0.815 -0.6873 0.429 3.0421 2.9964 3.6272 3.5763 0.3945 -0.6047 0.9511 1.1641 0.5562 -0.0127 -1.3813 3.8309 1.9904 2.133 1.458 2.9071 2.2961 2.0832 2.5972 1.0124 -0.3034 88 L3 + E1 TMS Br n-Bu O O N N N t-Bu t-Bu (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 Atom X 0 -4.054 2.3544 -2.0084 -0.8181 1.5785 -2.9283 -2.6556 -4.2954 -4.632 -5.0949 -2.7466 -2.1342 -2.7595 -3.8411 -1.947 -2.3979 Y 0 0.2985 0.9657 -0.0176 0.7342 -0.0857 -0.4707 -1.4965 -0.4568 -1.457 0.0483 0.394 0.8937 1.4136 1.5339 1.7647 2.1831 Z 0 -0.3209 -3.126 0.5447 -1.6236 -1.3068 1.6194 1.8963 0.8965 0.5977 1.4441 -0.4238 -1.6728 -2.7997 -2.8315 -3.8816 -4.7814 89 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 C28 C29 C30 C31 C32 H33 C34 H35 C36 F37 C38 H39 C40 H41 C42 C43 H44 C45 C46 Si47 H48 H49 C50 C51 C52 H53 H54 H55 H56 H57 H58 C59 C60 -0.5653 0.0821 -0.0423 1.3453 3.5437 3.9299 4.276 3.0164 3.4392 -2.8838 -1.5301 3.2855 2.5722 0.7024 1.8138 2.3509 2.2774 3.1448 1.6172 2.0607 0.5111 0.0186 0.0625 -0.8045 0.5696 1.9735 0.172 -0.2463 3.2032 5.0157 -1.2856 0.141 -0.2562 5.419 -1.135 -0.613 -0.7795 -2.1598 6.4755 4.7975 5.2466 6.0691 5.2617 1.5619 1.8019 1.0193 0.6168 0.5887 1.5051 0.1866 -0.4181 -0.2159 0.3928 0.2284 -1.9025 -2.8259 -1.0234 -0.7559 0.1863 -1.6818 -1.4742 -2.8958 -3.7966 -3.207 -4.1727 -2.261 -2.5196 2.1288 2.1996 1.8345 3.15 2.248 2.2415 2.805 3.2765 4.5105 3.9034 5.5325 4.3751 5.6503 5.1327 3.9346 4.0877 4.7198 1.9502 0.8428 -3.8301 -4.672 -2.6624 -2.3569 -2.372 -1.9138 -3.0766 -1.3313 -0.3393 2.9063 3.601 -1.6932 -0.7031 1.4296 2.2334 2.1357 3.1721 3.8004 3.2955 4.1944 2.5166 2.6387 1.593 0.979 0.855 0.8104 1.8291 0.1036 0.8258 1.2498 0.0183 -0.9186 0.8112 2.0157 0.0961 1.8455 -0.9408 0.0201 2.3225 2.904 1.2992 -0.2742 2.4756 90 H61 H62 H63 H64 H65 H66 C67 H68 H69 H70 H71 C72 C73 C74 C75 H76 H77 H78 H79 H80 H81 H82 H83 H84 H85 H86 H87 H88 H89 H90 H91 H92 H93 4.9968 4.6374 6.3137 5.8705 5.9154 7.1303 -1.1613 0.7757 -1.8027 -1.5429 -0.1524 -3.131 -3.9674 4.7982 2.8001 -1.5089 -1.3455 -0.702 2.8449 2.8478 1.4824 -3.1611 -2.3303 -4.0883 -3.8789 -4.9859 -3.8509 5.035 5.3699 5.1546 2.9876 1.7178 3.3173 -0.1252 0.9856 0.7937 2.6919 0.9438 2.033 6.8887 4.8889 7.604 6.7991 7.3234 1.8688 -0.1254 -2.1351 -2.225 0.8252 -0.8221 0.5507 -3.8703 -2.5967 -2.7371 2.459 2.2794 2.0233 0.3884 0.053 -1.2041 -3.1836 -1.5089 -1.9212 -3.2845 -2.0563 -1.6329 2.0249 3.3699 2.7949 -1.0613 -0.6894 0.0064 0.7911 0.8878 0.2577 1.8192 0.8506 2.5803 3.8644 -1.5848 -3.1119 4.5233 3.8659 2.9639 -0.9102 0.335 -0.7863 3.5065 1.951 2.0611 4.8314 3.4944 4.0458 -1.813 -2.2842 -0.5664 -3.3355 -3.2138 -3.8796 91 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 Atom X 0 -3.2466 1.0066 -1.4434 -1.1944 1.1839 -1.7402 -0.8253 -2.7897 -2.3595 -3.6612 -2.3445 -2.3043 -3.1912 -4.09 -2.8796 -3.556 -1.6984 -1.4255 -0.8626 0.4891 2.2432 2.0463 3.0061 2.5194 2.8173 -2.2217 Y 0 -1.2963 3.8889 -1.2851 1.282 1.6577 -2.7267 -3.2194 -2.677 -2.876 -3.3174 -0.6307 0.8468 1.7275 1.3626 3.0891 3.8122 3.5325 4.5864 2.5675 2.7133 3.5966 3.7674 4.2961 2.1167 1.5601 -3.4737 Z 0 -2.0756 0.0175 -0.7428 -0.8541 -0.03 -0.9409 -1.2915 -2.0731 -3.0625 -1.918 -1.3844 -1.4337 -2.0418 -2.5362 -1.9959 -2.4517 -1.3944 -1.374 -0.8458 -0.2662 0.7347 1.8004 0.384 0.4036 1.3014 0.3291 92 C28 C29 C30 C31 C32 H33 C34 H35 C36 F37 C38 H39 C40 H41 C42 C43 H44 C45 C46 Si47 H48 H49 C50 C51 C52 H53 H54 H55 H56 H57 H58 C59 C60 H61 H62 H63 H64 H65 H66 C67 H68 H69 H70 -1.1521 3.6031 3.6903 1.2727 1.9261 1.6604 2.94 3.4492 3.3032 4.2809 2.6857 3.0007 1.6738 1.2028 -0.9482 -2.3096 -0.6734 -0.1802 -3.4946 -5.3185 -0.4547 0.8965 -0.4331 -5.9792 0.3779 -0.1825 1.4486 0.128 -7.0246 -5.9569 -5.4038 -5.5772 -6.1343 -7.2234 -5.7539 -5.9434 -6.6539 -5.1368 -5.1259 0.1476 -1.5081 0.7445 -0.9101 -3.4111 1.9005 0.4155 -1.2498 -1.247 -0.5215 -2.1631 -2.1638 -3.0904 -3.976 -3.1298 -3.8708 -2.207 -2.2378 0.4425 0.6345 -0.5579 1.5857 0.8444 1.1232 2.5316 1.4383 1.7161 -0.1114 2.8463 0.7618 2.6717 3.7928 0.1335 -1.1299 -0.1136 2.8846 0.8577 0.9944 1.5715 -0.1605 3.1032 3.0499 3.6027 2.9875 1.8815 3.8062 3.1944 1.4212 -0.6863 -1.0457 0.6323 1.8684 2.6397 2.165 3.1298 1.1993 1.4739 -0.0436 -0.7796 -0.3112 -1.2971 2.1357 1.8476 2.4756 2.7485 1.5916 1.3609 2.2574 2.5915 4.2548 0.1127 4.8822 4.7465 4.6839 4.3749 -0.1293 0.5249 -0.8231 0.7723 3.0279 2.9461 3.7729 3.3974 0.7059 -0.2204 1.4725 6.3823 4.4313 6.8077 6.6031 93 H71 C72 C73 C74 C75 H76 H77 H78 H79 H80 H81 H82 H83 H84 H85 H86 H87 H88 H89 H90 H91 H92 H93 0.4207 -3.5286 -2.4314 4.9496 3.2851 -1.4804 -0.196 -0.9701 4.5218 3.8622 2.7689 -3.8426 -3.4071 -4.3487 -2.7323 -3.2169 -1.5028 5.7489 4.9597 5.1976 4.0593 2.322 3.2592 2.0635 -2.877 -4.9461 2.3473 2.7047 -3.9926 -3.8227 -2.3822 0.2522 -0.2056 0.0642 -3.4129 -1.8184 -2.9612 -5.5204 -5.0782 -5.3887 2.1841 3.4141 1.7694 2.5212 2.403 3.788 6.9136 0.8584 -0.0534 -0.1023 -1.9529 2.2939 1.0717 1.7464 -1.7456 -0.156 -1.5259 1.7651 1.1226 0.1316 0.8336 -0.8104 -0.4429 -0.8384 0.1619 0.8 -2.7106 -2.3904 -1.7697 94 L3 + E2 TMS Br O N Me O N N t-Bu t-Bu (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 Atom X 0 -4.0598 2.3544 -2.0172 -0.8212 1.5874 -2.9368 -2.6384 -4.295 -4.5998 -5.1149 -2.7543 -2.1406 -2.7691 -3.8532 -1.9571 -2.4106 -0.5717 Y 0 0.177 0.8449 -0.0458 0.6413 -0.1324 -0.4849 -1.4916 -0.5374 -1.5575 -0.0349 0.3059 0.7638 1.202 1.2912 1.5092 1.8629 1.341 Z 0 -0.3747 -3.1648 0.526 -1.6628 -1.301 1.6063 1.924 0.8685 0.6049 1.3876 -0.4663 -1.7309 -2.8906 -2.937 -3.9858 -4.9117 -3.9142 95 H19 C20 C21 C22 H23 H24 C25 H26 C27 C28 C29 C30 C31 C32 H33 C34 H35 C36 F37 C38 H39 C40 H41 C42 C43 H44 C45 C46 Si47 H48 H49 C50 H51 H52 H53 C54 C55 H56 H57 H58 H59 H60 H61 0.0763 -0.0451 1.3478 3.5462 3.9157 4.2884 3.0302 3.4463 -2.9305 -1.577 3.3225 2.623 0.7024 1.7947 2.3183 2.2567 3.11 1.6145 2.0577 0.5268 0.0479 0.0793 -0.772 0.5312 1.9392 0.1128 -0.2498 3.1674 4.9784 -1.3188 0.1265 5.3715 6.4271 4.7472 5.1968 6.0367 5.232 4.9702 4.6093 6.2849 5.8358 5.8899 7.0968 1.5431 0.8803 0.5172 0.5221 1.4647 0.1003 -0.4444 -0.1917 0.4258 0.3315 -1.9397 -2.8256 -0.9589 -0.6536 0.2942 -1.5498 -1.3135 -2.7714 -3.6442 -3.1189 -4.0895 -2.2025 -2.4907 2.1548 2.2213 1.92 3.1446 2.2753 2.2908 2.9018 3.2184 3.9747 4.0194 4.1801 4.7706 1.9657 0.9264 -0.0542 1.09 0.8904 2.6856 0.948 2.0618 -4.7655 -2.7134 -2.383 -2.3898 -1.9723 -3.0721 -1.3064 -0.3232 2.8603 3.5685 -1.5995 -0.5663 1.4739 2.2896 2.1775 3.2577 3.895 3.3987 4.3248 2.6095 2.746 1.6562 1.0334 0.7522 0.7345 1.7334 -0.0724 0.7689 1.199 -0.0976 -1.1011 1.9208 2.2287 2.8024 1.1821 -0.3149 2.4612 2.0367 3.353 2.7791 -1.1216 -0.704 -0.0343 96 C62 C63 C64 C65 H66 H67 H68 H69 H70 H71 H72 H73 H74 H75 H76 H77 H78 H79 H80 H81 H82 H83 H84 -3.2212 -4.0047 4.8384 2.8424 -1.5837 -1.357 -0.7565 2.9147 2.8912 1.5322 -3.2734 -2.4299 -4.1806 -3.9441 -5.0251 -3.8527 5.0902 5.4011 5.192 3.0493 1.7571 3.3482 -0.1584 1.8798 -0.0913 -2.1443 -2.3359 0.9577 -0.7027 0.6633 -3.8741 -2.54 -2.7605 2.504 2.2891 1.985 0.4634 0.0361 -1.1573 -3.1993 -1.5456 -1.875 -3.4008 -2.1921 -1.77 4.1467 2.4773 3.8293 -1.4812 -3.0012 4.4713 3.868 2.9261 -0.7203 0.4597 -0.6561 3.3799 1.8349 1.9495 4.7756 3.4434 4.0548 -1.6573 -2.2114 -0.475 -3.1762 -3.1095 -3.7958 0.3781 (S)-Transition State Calculated geometry Ni1 Atom X 0 Y 0 Z 0 97 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 C28 C29 C30 C31 C32 H33 C34 H35 C36 F37 C38 H39 C40 H41 C42 C43 H44 -3.2407 1.0346 -1.445 -1.1866 1.1942 -1.7454 -0.8301 -2.7878 -2.3521 -3.6619 -2.3401 -2.2939 -3.171 -4.0673 -2.8525 -3.5212 -1.6721 -1.3915 -0.8463 0.5065 2.274 2.0864 3.0396 2.5363 2.8366 -2.2351 -1.1764 3.6099 3.6845 1.2711 1.9401 1.6814 2.9627 3.4851 3.3184 4.3051 2.6846 2.994 1.6645 1.1825 -0.937 -2.3018 -0.6514 -1.3341 3.8847 -1.3017 1.2645 1.652 -2.746 -3.2481 -2.7157 -2.9349 -3.3511 -0.6576 0.8183 1.6852 1.3101 3.0458 3.7586 3.5001 4.5521 2.5474 2.7034 3.6094 3.8218 4.2894 2.1159 1.5897 -3.4671 -3.3709 1.8533 0.3565 -1.2338 -1.1857 -0.4344 -2.0861 -2.0509 -3.0438 -3.9138 -3.1288 -3.8927 -2.2206 -2.2862 0.4972 0.6569 -0.4865 -2.0717 -0.1146 -0.729 -0.895 -0.0798 -0.9007 -1.2364 -2.0399 -3.0226 -1.8779 -1.3885 -1.4716 -2.1127 -2.6041 -2.1054 -2.5881 -1.5106 -1.5225 -0.9261 -0.3519 0.6047 1.6643 0.2229 0.327 1.2421 0.3809 1.4812 -0.7635 -1.073 0.665 1.8916 2.64 2.2058 3.1628 1.2672 1.5584 0.0349 -0.6798 -0.2508 -1.2295 2.1127 1.8082 2.4892 98 C45 C46 Si47 H48 H49 C50 H51 H52 H53 C54 C55 H56 H57 H58 H59 H60 H61 C62 C63 C64 C65 H66 H67 H68 H69 H70 H71 H72 H73 H74 H75 H76 H77 H78 H79 H80 H81 H82 H83 H84 -0.2057 -3.4876 -5.3096 -0.4723 0.882 -5.9728 -7.0137 -5.9649 -5.3911 -5.5535 -6.1352 -7.2233 -5.7557 -5.9499 -6.6282 -5.103 -5.1043 -3.5511 -2.4318 4.9643 3.2874 -1.5099 -0.2152 -1.0031 4.5097 3.859 2.7576 -3.8676 -3.4402 -4.3647 -2.7417 -3.2066 -1.4961 5.756 4.984 5.2163 4.0537 2.3185 3.2718 -0.4826 1.6761 0.8437 1.1249 2.6151 1.5461 -0.1194 0.1337 -1.1325 -0.1405 2.8809 0.8833 1.0231 1.6047 -0.131 3.1048 3.0322 3.6043 -2.8682 -4.9487 2.3098 2.6148 -3.9313 -3.7865 -2.3325 0.1643 -0.2357 -0.0041 -3.3836 -1.8025 -2.9782 -5.5051 -5.1011 -5.3948 2.1171 3.3845 1.7598 2.3979 2.3054 3.7042 1.7889 2.6983 1.5412 1.2963 2.1957 2.6604 0.0592 -0.1935 0.4847 -0.8723 0.6854 2.9621 2.8731 3.7002 3.3449 0.6068 -0.3051 1.3814 0.8845 0.029 -0.2057 -2.0551 2.3656 1.1512 1.7808 -1.773 -0.1644 -1.535 1.8022 1.1227 0.154 0.9243 -0.7353 -0.3387 -0.9428 0.0237 0.7128 -2.8122 -2.4737 -1.9109 3.7596 99 L4 + E1 TMS Br n-Bu O O N N N Ph Ph (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 Atom X 0 -3.9786 2.4127 -1.9423 -0.7464 1.5814 -2.7959 -2.6629 -4.2112 -4.736 -4.8444 -2.6878 -2.0574 -2.6405 -3.7151 -1.7952 -2.214 -0.426 Y 0 0.6009 0.6167 -0.0776 0.8344 -0.0518 -0.4505 -1.5189 -0.1694 -1.0861 0.4268 0.512 1.041 1.6029 1.7707 1.9208 2.3643 1.6424 Z 0 -0.1932 -3.1545 0.4344 -1.5969 -1.1904 1.5796 1.7836 1.0241 0.7316 1.6873 -0.4308 -1.662 -2.7914 -2.842 -3.8591 -4.7624 -3.7987 100 H19 C20 C21 C22 H23 H24 C25 H26 C27 C28 H29 C30 H31 C32 F33 C34 H35 C36 H37 C38 C39 H40 C41 C42 Si43 H44 H45 C46 C47 C48 H49 H50 H51 H52 H53 H54 C55 C56 H57 H58 H59 H60 H61 0.2366 0.0591 1.4079 3.5161 4.3533 3.791 2.9548 3.4823 0.6398 1.5797 2.0134 2.0018 2.7373 1.4783 1.8957 0.5433 0.1589 0.1304 -0.6056 0.3912 1.7884 0.0309 -0.4863 3.013 4.8459 -1.5251 -0.1798 -0.458 5.2198 -1.4476 -0.6849 -1.2256 -2.4613 6.2964 4.6738 4.9312 5.7599 5.2874 5.0243 4.7469 6.3666 5.376 5.6829 1.8421 1.0762 0.5522 -0.0999 0.5981 -0.9292 -0.5697 -0.0837 -1.1343 -0.857 0.1383 -1.8406 -1.6285 -3.1195 -4.0797 -3.4413 -4.4601 -2.4393 -2.7004 1.9945 2.131 1.5606 3.059 2.243 2.3616 2.7031 3.2667 4.3643 4.0708 5.3975 4.1421 5.6006 4.9632 4.1747 4.2525 4.8484 2.0791 1.023 0.0294 1.17 1.031 2.7239 1.031 -4.6394 -2.6257 -2.31 -2.5257 -2.4342 -3.1867 -1.1562 -0.3259 1.3706 2.3673 2.4589 3.2649 4.0424 3.1495 3.9999 2.1761 2.112 1.2958 0.53 1.1346 1.0465 2.0728 0.5265 1.0071 1.2731 0.4937 -0.51 1.3297 1.9456 0.8002 2.3842 -0.2605 0.8177 2.1487 2.8826 1.2232 -0.3411 2.5115 2.1195 3.4582 2.726 -1.145 -0.6636 101 H62 C63 H64 H65 H66 H67 C68 C69 C70 C71 C72 C73 H74 H75 H76 H77 H78 C79 C80 C81 C82 C83 C84 H85 H86 H87 H88 H89 6.8285 -1.4327 0.5632 -2.1565 -1.6835 -0.4383 -1.4592 -2.2829 -2.7397 -2.3818 -1.5659 -1.104 -1.0988 -2.5701 -3.3756 -1.2772 -0.463 2.9346 3.6307 3.6462 2.9642 2.2682 2.2527 2.9204 4.1575 4.1805 1.7259 1.7066 (S)-Transition State 2.3045 6.7001 4.7778 7.4245 6.5236 7.17 1.8313 2.4289 1.6881 0.343 -0.2523 0.4891 2.4118 3.4765 2.1722 -1.2989 0.0149 -4.8323 -3.9956 -2.6179 -2.0674 -2.9109 -4.2873 -5.91 -4.4144 -1.9616 -2.4911 -4.938 -0.2048 1.5912 1.3141 1.1924 2.648 1.5627 4.9855 4.03 2.9417 2.8015 3.7664 4.8534 5.8362 4.1314 2.1969 3.6567 5.5981 -0.5065 0.3641 0.1464 -0.9384 -1.8105 -1.5966 -0.3361 1.2229 0.8346 -2.6617 -2.2816 102 Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 C28 H29 C30 H31 C32 F33 C34 H35 C36 H37 C38 C39 Atom X 0 -3.3405 1.2889 -1.3581 -1.1577 1.1663 -1.6201 -0.9233 -3.0709 -3.1987 -3.8062 -2.3429 -2.2762 -3.1235 -4.0368 -2.7465 -3.3869 -1.5429 -1.2177 -0.7594 0.6049 2.591 2.6989 3.3562 2.543 2.6724 1.2733 1.7719 1.3808 2.7869 3.1785 3.307 4.2935 2.8451 3.2835 1.8279 1.468 -1.0101 -2.3693 Y 0 -1.2686 3.7907 -1.204 1.3175 1.5873 -2.6473 -3.0348 -2.6586 -3.2624 -2.9548 -0.572 0.9046 1.8034 1.4635 3.1497 3.8856 3.5618 4.6005 2.5843 2.6708 3.4458 3.9935 3.7704 1.9058 1.6441 -1.298 -1.591 -1.0872 -2.5351 -2.7699 -3.1807 -4.0854 -2.9189 -3.4434 -1.9787 -1.7765 0.1714 0.3882 Z 0 -1.8327 -0.2492 -0.8026 -0.8327 0.1001 -0.9465 -1.7024 -1.4871 -2.39 -0.7293 -1.3333 -1.4168 -2.054 -2.5399 -2.0572 -2.5434 -1.4754 -1.5071 -0.874 -0.3031 0.3122 1.2541 -0.4009 0.5052 1.5627 0.5092 1.7808 2.6665 1.9655 2.9562 0.8548 1.0229 -0.4273 -1.2772 -0.5855 -1.5982 2.0877 1.798 103 H40 C41 C42 Si43 H44 H45 C46 C47 C48 H49 H50 H51 H52 H53 H54 C55 C56 H57 H58 H59 H60 H61 H62 C63 H64 H65 H66 H67 C68 C69 C70 C71 C72 C73 H74 H75 H76 H77 H78 C79 C80 C81 C82 -0.7612 -0.2452 -3.5542 -5.3792 -0.4563 0.833 -0.5781 -5.9897 0.2308 -0.3886 1.305 0.0458 -7.0781 -5.779 -5.5108 -5.6735 -6.205 -7.2948 -5.8362 -6.007 -6.7528 -5.2017 -5.2684 -0.0866 -1.6556 0.5118 -1.1479 0.1194 -0.9 -1.865 -2.1169 -1.3988 -0.4432 -0.1937 -0.7011 -2.4226 -2.8632 0.1237 0.5605 5.3491 5.3856 4.4839 3.54 -0.8642 1.2413 0.5802 0.8251 2.2268 1.0645 1.279 -0.4196 2.3328 0.2848 2.1307 3.3196 -0.3203 -1.447 -0.2753 2.5825 0.5347 0.6618 1.2449 -0.4848 2.7711 2.7676 3.3083 2.3846 1.4715 3.1493 2.619 1.4177 -4.7413 -3.7336 -3.0716 -3.4043 -4.42 -5.0883 -5.258 -3.4595 -2.2753 -4.6769 -5.8759 -0.378 -0.4426 0.3044 1.1178 2.3319 2.8256 1.528 1.289 2.3834 2.7124 4.3212 0.0269 5.0719 4.7583 4.9264 4.6162 -0.1028 0.3596 -0.9507 0.7033 2.9477 2.86 3.702 3.3097 0.5993 -0.2717 1.4235 6.5617 4.4499 7.0763 6.7328 7.0445 2.7486 2.6943 1.4943 0.3419 0.3992 1.5973 3.6889 3.5913 1.4615 -0.4971 1.6324 -1.841 -0.4492 0.3088 -0.3177 104 C83 C84 H85 H86 H87 H88 H89 3.5077 4.4076 6.0522 6.1124 4.5028 2.7695 4.375 1.1811 0.4366 -0.9639 -1.0849 0.2416 1.8105 0.491 -1.7148 -2.4739 -2.4352 0.0505 1.3982 -2.2184 -3.5633 105 L4 + E2 TMS Br O N Me O N N Ph Ph (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 Atom X 0 -3.9846 2.4003 -1.9442 -0.7539 1.5771 -2.7949 -2.6683 -4.213 -4.7623 -4.8228 -2.6933 -2.0669 -2.6571 -3.7333 -1.8172 -2.2418 Y 0 0.5757 0.587 -0.0865 0.8169 -0.0673 -0.4726 -1.546 -0.1712 -1.0805 0.4489 0.4934 1.0118 1.5465 1.7037 1.8492 2.2707 Z 0 -0.1957 -3.1725 0.4358 -1.6043 -1.2003 1.5781 1.7598 1.0368 0.768 1.7002 -0.4324 -1.6705 -2.8095 -2.8609 -3.8858 -4.797 106 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 C28 H29 C30 H31 C32 F33 C34 H35 C36 H37 C38 C39 H40 C41 C42 Si43 H44 H45 C46 H47 H48 H49 C50 C51 H52 H53 H54 H55 H56 H57 C58 C59 C60 -0.446 0.2126 0.0464 1.3981 3.5099 4.3408 3.7927 2.9525 3.4787 0.6437 1.569 1.9885 1.9943 2.719 1.4883 1.9104 0.5667 0.1959 0.1504 -0.5744 0.3815 1.7835 0.0096 -0.4695 3.0086 4.8408 -1.5284 -0.1409 5.2269 6.3035 4.6783 4.9491 5.7623 5.2642 4.9928 4.7213 6.3426 5.3936 5.673 6.8329 -1.407 -2.2037 -2.682 1.5813 1.7668 1.0423 0.5264 -0.1152 0.591 -0.9466 -0.5797 -0.0867 -1.13 -0.8535 0.1459 -1.8442 -1.6334 -3.1277 -4.0944 -3.448 -4.4705 -2.4396 -2.6994 1.9864 2.1118 1.5668 3.0603 2.2147 2.323 2.7775 3.3077 4.0388 4.1358 4.24 4.8079 2.0095 0.9999 0.0028 1.1672 1.0008 2.6519 0.9595 2.2214 1.7265 2.3612 1.6452 -3.8238 -4.6708 -2.6411 -2.3244 -2.5384 -2.4516 -3.1934 -1.1655 -0.3388 1.3718 2.3816 2.4914 3.2701 4.0579 3.132 3.9726 2.1454 2.0636 1.2744 0.4974 1.113 1.0414 2.0526 0.4874 1.0145 1.2902 0.4622 -0.5308 1.9385 2.1452 2.87 1.203 -0.3143 2.5515 2.1744 3.4933 2.7706 -1.1274 -0.6275 -0.1723 5.0161 4.0614 2.9659 107 C61 C62 C63 H64 H65 H66 H67 H68 C69 C70 C71 C72 C73 C74 H75 H76 H77 H78 H79 H80 -2.3673 -1.5772 -1.0982 -1.0306 -2.4528 -3.2978 -1.3198 -0.4776 2.96 3.6478 3.6536 2.9699 2.2817 2.2761 2.9537 4.1756 4.182 1.7382 1.7364 -0.4043 0.2907 -0.3407 0.374 2.2867 3.4179 2.1557 -1.3944 -0.1285 -4.8385 -3.9918 -2.6152 -2.076 -2.9296 -4.3049 -5.9154 -4.4017 -1.9511 -2.5187 -4.9636 3.9831 2.8138 3.7768 4.8742 5.8735 4.1694 2.2221 3.6564 5.6177 -0.4906 0.3767 0.151 -0.9384 -1.8069 -1.5851 -0.3142 1.2392 0.8362 -2.6617 -2.2674 1.0874 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 Atom X 0 -3.3689 1.3125 -1.373 Y 0 -1.2746 3.7782 -1.2084 Z 0 -1.7802 -0.3425 -0.7767 108 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 H17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 C28 H29 C30 H31 C32 F33 C34 H35 C36 H37 C38 C39 H40 C41 C42 Si43 H44 H45 C46 H47 -1.1615 1.1783 -1.645 -0.9601 -3.1025 -3.2453 -3.8298 -2.3611 -2.2875 -3.1351 -4.0543 -2.7501 -3.3904 -1.5379 -1.2057 -0.755 0.6182 2.6209 2.7459 3.3771 2.5667 2.7212 1.2746 1.8003 1.4308 2.8155 3.2291 3.307 4.2937 2.8166 3.2331 1.8003 1.4183 -0.9602 -2.3256 -0.7156 -0.1991 -3.5137 -5.3413 -0.391 0.8809 -5.9827 -7.0725 1.3131 1.5841 -2.6519 -3.0531 -2.6617 -3.276 -2.9443 -0.5775 0.8973 1.7901 1.4472 3.1339 3.8653 3.548 4.5835 2.576 2.6634 3.435 3.9972 3.7436 1.8985 1.6517 -1.3002 -1.5909 -1.083 -2.5387 -2.7721 -3.1899 -4.0977 -2.9302 -3.4591 -1.9861 -1.7848 0.2027 0.4169 -0.8301 1.2817 0.6069 0.8585 2.274 1.094 -0.4082 -0.3035 -0.8387 0.0572 -0.8987 -1.6583 -1.4208 -2.3144 -0.6502 -1.3024 -1.4064 -2.0515 -2.5238 -2.0814 -2.5745 -1.5192 -1.5735 -0.908 -0.3588 0.2049 1.1362 -0.5245 0.4238 1.4813 0.4969 1.7576 2.6501 1.9215 2.9036 0.801 0.9488 -0.471 -1.3292 -0.6086 -1.6135 2.0911 1.814 2.3496 2.8167 1.5599 1.3476 2.3881 2.7985 0.1234 0.0102 109 H48 H49 C50 C51 H52 H53 H54 H55 H56 H57 C58 C59 C60 C61 C62 C63 H64 H65 H66 H67 H68 C69 C70 C71 C72 C73 C74 H75 H76 H77 H78 H79 H80 -5.7738 -5.5195 -5.6354 -6.1402 -7.2306 -5.7552 -5.9413 -6.7154 -5.1824 -5.2112 -0.8928 -1.8551 -2.1168 -1.4117 -0.4585 -0.1991 -0.6864 -2.4032 -2.8608 0.0984 0.553 5.294 5.367 4.4909 3.5364 3.4677 4.3419 5.9768 6.1021 4.5386 2.7212 4.2809 -0.5086 -1.43 -0.2877 2.6046 0.6112 0.7422 1.3372 -0.4004 2.7982 2.7646 3.3437 -4.7073 -3.697 -3.0467 -3.3942 -4.4121 -5.0685 -5.2148 -3.4124 -2.2484 -4.6804 -5.8582 -0.4401 -0.4848 0.2796 1.0909 1.1343 0.3724 -1.0398 -1.1255 0.2323 1.7619 0.4115 1.3153 0.474 -0.8651 0.7286 3.0262 2.954 3.7571 3.4093 0.6421 -0.2596 1.4239 2.8119 2.7566 1.5523 0.3962 0.4548 1.6574 3.7556 3.6561 1.5186 -0.4443 1.6933 -1.9622 -0.5712 0.1996 -0.4134 -1.81 -2.5817 -2.5662 -0.0815 1.2889 -2.3035 -3.6706 3.8745 110 L5 + E2 TMS Br O O N N N Me (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 C8 C9 H10 C11 H12 C13 H14 Atom X 0 -2.6775 3.6117 -1.8605 0.5129 1.707 -1.6746 -0.3551 -0.016 -0.7392 1.272 1.5801 2.1519 3.1389 Y 0 2.4729 -0.6704 0.8722 1.0128 -1.0145 1.725 1.8378 2.6008 3.2773 2.4455 3.0274 1.5161 1.3364 Z 0 -1.9708 -1.7709 -0.62 -1.6434 -0.6381 -1.5604 -2.2148 -3.3265 -3.7789 -3.8445 -4.7133 -3.2846 -3.7068 111 C15 C16 C17 C18 H19 C20 H21 C22 F23 C24 H25 C26 H27 C28 C29 H30 C31 C32 Si33 H34 H35 C36 H37 H38 H39 C40 C41 H42 H43 H44 H45 H46 H47 C48 C49 C50 H51 H52 H53 H54 C55 C56 C57 1.7124 2.371 -0.4531 0.3163 1.2258 -0.055 0.5357 -1.2066 -1.5692 -1.9921 -2.8882 -1.6037 -2.2161 0.6648 2.0871 0.4885 -0.0108 3.2625 4.9966 -1.0882 0.1693 5.2212 6.233 5.0847 4.4957 5.2014 6.2203 6.1286 6.0718 7.2479 4.4654 5.079 6.2068 -3.2665 -3.8483 -4.403 -4.0113 -5.4979 -4.56 -3.7726 -3.9777 -3.4046 -2.9962 0.804 -0.3283 -1.1375 -1.5297 -0.9874 -2.6322 -2.9569 -3.3316 -4.3908 -2.9684 -3.5424 -1.8632 -1.5887 1.3531 1.4581 0.9975 2.7108 1.6691 2.2324 2.6598 3.1213 3.8985 4.2876 3.8199 4.6303 2.4096 0.9877 0.0132 0.8371 1.3499 3.1156 1.4422 2.7939 1.0314 2.0676 3.2494 4.1966 3.2918 1.6467 0.0589 2.9762 1.7104 1.2378 -2.1748 -1.4924 1.4156 2.5124 2.7789 3.2823 4.1395 2.9399 3.6827 1.8559 1.6182 1.0935 0.2323 1.2951 1.0373 2.3134 1.0981 0.7723 0.4092 1.2734 0.096 1.2426 1.0513 2.331 0.8578 -1.4475 1.0927 0.5928 2.1719 0.9371 -1.8602 -1.9536 -1.6779 -0.1912 -1.2006 -0.4044 -0.7996 -0.4891 -1.9184 -0.2296 1.0168 1.1536 2.3997 112 C58 C59 C60 H61 H62 H63 H64 C65 C66 C67 H68 H69 C70 C71 C72 C73 C74 C75 H76 H77 H78 H79 H80 H81 H82 -3.1418 -3.6931 -4.1217 -2.5543 -2.8189 -3.7951 -4.563 3.9259 2.5831 4.2598 4.4744 5.1586 2.1294 3.0434 2.7785 1.5923 0.6837 0.9473 3.4863 1.3717 -0.2375 0.2413 2.6696 4.7427 0.4099 (S)-Transition State Calculated geometry 2.0672 3.3457 3.805 0.2472 1.7182 3.9875 4.7979 -1.8272 -2.106 -3.0504 -2.7488 -3.5539 -3.4392 -3.9371 -5.1316 -5.8124 -5.3122 -4.118 -5.5271 -6.7455 -5.8586 -3.7207 -2.0928 -1.5168 3.4293 3.5109 3.3739 2.1287 2.5018 4.4927 4.2505 2.026 -0.9332 -0.1951 -1.7904 -2.8247 -1.408 -0.7427 -1.6722 -2.3412 -2.0649 -1.1257 -0.4552 -3.0719 -2.5861 -0.9177 0.2746 0.8985 -0.2757 1.8174 113 Ni1 O2 O3 N4 N5 N6 C7 C8 C9 H10 C11 H12 C13 H14 C15 C16 C17 C18 H19 C20 H21 C22 F23 C24 H25 C26 H27 C28 C29 H30 C31 C32 Si33 H34 H35 C36 H37 H38 H39 C40 C41 H42 Atom X 0 -3.3703 1.3094 -1.3986 -1.1152 1.233 -2.3482 -2.2376 -3.0667 -3.983 -2.6694 -3.2958 -1.4606 -1.1155 -0.6966 0.6608 1.2086 1.9007 1.6774 2.9 3.4419 3.2082 4.1715 2.5487 2.8204 1.5525 1.0567 -1.0199 -2.3892 -0.6824 -0.3902 -3.5806 -5.4022 -0.6683 0.703 -6.127 -7.1857 -6.0749 -5.5976 -5.6102 -6.1916 -7.2788 Y 0 -1.1623 3.8131 -1.1891 1.3405 1.5905 -0.5165 0.9555 1.8728 1.5499 3.2128 3.9639 3.5969 4.6293 2.6005 2.6763 -1.3167 -1.2963 -0.5378 -2.2281 -2.212 -3.1941 -4.0943 -3.2565 -4.0273 -2.3142 -2.357 0.2847 0.3544 -0.685 1.4976 0.4739 0.7893 2.4236 1.4226 -0.3393 -0.0857 -1.3876 -0.2488 2.5891 0.4417 0.6056 Z 0 -1.9057 -0.2114 -0.8424 -0.868 0.0635 -1.3897 -1.463 -2.0976 -2.5892 -2.0879 -2.569 -1.4988 -1.5185 -0.9034 -0.3201 0.6173 1.8347 2.5876 2.1264 3.0729 1.1781 1.4488 -0.0413 -0.7636 -0.3082 -1.2805 2.075 1.7505 2.4423 2.7096 1.4726 1.2879 2.1892 2.7397 -0.0187 -0.1803 0.3073 -0.9767 0.7996 2.9531 2.9056 114 H43 H44 H45 H46 H47 C48 C49 C50 H51 H52 C53 C54 C55 H56 H57 H58 H59 H60 H61 C62 C63 C64 C65 C66 C67 H68 H69 H70 H71 C72 C73 C74 C75 C76 C77 H78 H79 H80 H81 H82 -5.7782 -6.0143 -6.6781 -5.1366 -5.1577 -1.8231 -3.0634 -4.1897 -5.1531 -4.2845 2.6002 2.5942 3.7554 3.4072 4.5335 -2.8704 -1.0095 2.7773 2.5971 -3.7347 -2.383 -1.7262 -2.4575 -3.8199 -4.4651 -0.6633 -1.9635 -4.3812 -5.5231 3.6597 4.2734 5.2694 5.6421 5.0359 4.0408 5.7532 6.4187 5.3446 3.5719 -0.7398 1.0976 -0.602 2.8418 2.7944 3.2549 -2.5985 -2.5916 -3.3263 -2.8252 -4.3426 3.5047 1.9485 3.9273 4.6352 4.4389 -2.9467 -3.2381 1.5627 4.007 -3.3733 -3.0417 -3.1072 -3.4703 -3.7694 -3.734 -2.8741 -3.5199 -4.0463 -3.9897 1.5219 2.6328 2.4609 1.1669 0.0569 0.2269 3.3254 1.0195 -0.9499 -0.6364 1.5929 3.7329 3.2521 0.7171 -0.1712 1.5489 -0.855 -1.7903 -1.0744 -1.2275 -1.484 0.4097 0.4931 -0.4983 -1.2627 0.0851 -2.8086 -1.2149 1.5035 1.3823 0.364 0.4791 1.7048 2.8357 2.7324 1.495 1.7768 3.8073 3.6262 1.4146 -0.4945 -1.0765 -2.0374 -2.4018 -1.8043 -0.8422 -2.4954 -3.1541 -2.0901 -0.3735 3.751 115 OMe L6 + E1 TMS Br O n-Bu O N N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 Atom X 0 -4.0046 2.3852 -1.9496 -0.753 1.6006 -2.8144 -2.6211 -4.2303 -4.7279 -4.896 -2.7028 -2.0733 -2.6696 -3.7467 -1.8345 -0.4505 0.2257 Y 0 0.4291 0.5892 -0.0836 0.7852 -0.0648 -0.5766 -1.65 -0.3479 -1.2772 0.2315 0.4405 0.9599 1.4488 1.5852 1.7462 1.4906 1.6439 Z 0 -0.2784 -3.2044 0.4366 -1.6136 -1.2134 1.5196 1.6438 0.9368 0.6375 1.5843 -0.4623 -1.6988 -2.8401 -2.9193 -3.943 -3.8625 -4.6998 116 C19 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 0.0316 1.3947 3.5211 4.3358 3.8176 2.9958 3.5098 -2.5161 -1.4324 -2.8325 -3.9159 -2.3734 -2.4523 -3.2423 -2.9569 -4.3346 -3.0015 3.1152 2.7301 4.5847 5.0271 4.6866 5.1815 2.2666 2.3534 2.587 1.2037 0.6159 1.5557 1.9828 1.9962 2.7332 1.4858 1.9117 0.5443 0.1626 0.115 -0.622 0.4565 1.8618 0.0147 -0.3162 3.0905 0.994 0.5085 -0.0718 0.6568 -0.9016 -0.5233 0.0229 0.1167 -0.0105 1.6103 1.7967 2.1206 2.0899 -0.6033 -1.6639 -0.5508 -0.1428 -2.0265 -2.1594 -2.4456 -2.3659 -3.4914 -1.8239 -2.8795 -3.941 -2.7807 -2.6062 -1.1377 -0.8933 0.1007 -1.9116 -1.7247 -3.191 -4.1788 -3.4795 -4.4966 -2.4443 -2.6823 2.0184 2.0865 1.6629 3.0894 2.1315 -2.6613 -2.3429 -2.5748 -2.5185 -3.2265 -1.1881 -0.3864 2.8561 3.0072 2.8394 2.802 1.9828 3.7514 3.9909 4.0379 3.8632 4.9585 -0.8958 0.1252 -0.9022 -1.9069 -0.5822 -0.2194 -1.8341 -1.5649 -2.8828 -1.7739 1.3827 2.39 2.5183 3.2404 4.0229 3.0741 3.8858 2.0959 1.9961 1.2623 0.4896 1.059 1.0704 1.9951 0.3292 1.1121 117 Si62 H63 H64 C65 C66 C67 H68 H69 H70 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 O87 C88 H89 H90 H91 4.9171 -1.3519 0.1218 -0.3558 5.375 -1.1881 0.6729 -0.768 -0.7711 -1.2542 -2.2074 -1.8582 -0.2498 -1.7007 6.4481 4.809 5.1633 5.8592 5.2369 4.8947 4.7068 6.3123 5.5563 5.7043 6.9377 -2.4413 -1.6777 -2.3885 -0.917 -1.198 (S)-Transition State 2.0684 2.7598 3.261 4.4111 3.562 5.4779 4.7754 4.2258 5.6535 6.7918 5.0888 7.5414 7.2155 6.6456 3.5426 3.5739 4.4963 2.0817 0.4728 -0.3991 0.4711 0.351 2.9273 1.1508 2.1738 2.2249 2.5158 2.8985 3.28 1.6063 1.4382 0.168 -0.6657 1.1046 2.4739 0.3993 1.2564 2.1102 -0.606 1.1688 0.2387 0.6387 1.3174 2.1638 2.7175 3.4166 1.9338 -0.184 2.3732 1.7967 3.3371 2.5727 -0.8186 -0.7474 0.0149 -5.0185 -6.1875 -6.925 -5.9757 -6.5752 118 Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 Atom X 0 -3.2744 1.1749 -1.3507 -1.1713 1.1489 -1.5837 -0.7384 -2.872 -2.7049 -3.7023 -2.322 -2.2856 -3.1526 -4.0578 -2.8283 -1.6199 -1.3014 -0.8184 0.5424 2.4621 2.465 3.2408 2.5146 2.6916 -1.6527 -0.7362 -2.8553 -2.7599 -3.7973 -2.9467 -1.6041 -0.6975 -2.4764 -1.6103 3.5588 3.4167 4.9708 5.1219 Y 0 -1.3347 3.844 -1.2421 1.2835 1.6342 -2.6878 -3.1061 -2.7309 -3.1165 -3.2721 -0.6255 0.8527 1.7196 1.3767 3.0955 3.5299 4.5692 2.5597 2.6932 3.5599 4.054 3.996 2.0155 1.7021 -3.4105 -3.1088 -2.9948 -3.3965 -3.3853 -1.9039 -4.9222 -5.2203 -5.2723 -5.4508 1.3278 0.2495 1.6932 1.4612 Z 0 -1.9449 -0.2679 -0.8091 -0.8583 0.0692 -0.9539 -1.5163 -1.8138 -2.8253 -1.3486 -1.3791 -1.4486 -2.0756 -2.5736 -2.0636 -1.4833 -1.496 -0.9017 -0.3302 0.3579 1.3358 -0.2766 0.4551 1.4925 0.3981 0.9284 1.2414 2.2595 0.8278 1.3194 0.1829 -0.363 -0.3909 1.1457 -0.4399 -0.2747 0.0144 1.0784 119 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 C66 C67 H68 H69 H70 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 5.182 5.7164 3.3401 3.4465 2.3441 4.0835 1.2814 1.8256 1.4663 2.8422 3.2657 3.3184 4.296 2.8115 3.2108 1.7947 1.404 -0.9631 -2.3032 -0.7925 -0.1315 -3.4681 -5.2777 -0.3253 0.9354 -0.4058 -5.908 0.4662 -0.2323 -1.4706 1.5264 0.2163 0.2911 0.8583 0.4161 -0.8293 -6.9866 -5.7519 -5.3978 -5.5261 -6.1318 -7.2163 -5.7512 2.7632 1.1306 1.6132 2.6841 1.2882 1.0751 -1.2912 -1.5428 -1.0069 -2.4846 -2.6838 -3.1807 -4.0916 -2.9655 -3.5308 -2.022 -1.8559 0.2251 0.5476 -0.8262 1.2357 0.8345 1.1352 2.2441 1.0327 1.2187 -0.1887 2.2116 0.2006 1.4385 1.9872 2.198 3.2244 2.9204 1.2033 2.4511 -0.0571 -1.1886 -0.1583 2.8552 0.995 1.1458 1.7504 -0.1333 -0.5635 -1.9237 -2.1559 -2.2568 -2.5274 0.5257 1.7895 2.6694 1.9755 2.9608 0.8741 1.0455 -0.4001 -1.2433 -0.559 -1.5671 2.088 1.7995 2.3388 2.84 1.529 1.2464 2.4449 2.6779 4.3473 0.0765 5.1105 4.7338 4.5273 4.907 6.614 4.7116 7.1372 7.0397 6.8445 -0.0981 0.508 -0.8957 0.5385 2.9105 2.7988 3.6135 120 H83 H84 H85 H86 O87 C88 H89 H90 H91 -5.9668 -6.6024 -5.1112 -5.0562 -3.7133 -3.4625 -4.3255 -3.3719 -2.5505 0.0013 3.079 2.9591 3.613 3.9028 5.3064 5.7566 5.7077 5.5252 3.3518 0.4825 -0.4728 1.1827 -2.6324 -2.6644 -3.1624 -1.6456 -3.237 121 L6 + E2 OMe TMS Br O Me O N N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 Atom X 0 -4.0163 2.3716 -1.9519 -0.7679 1.6041 -2.8088 -2.5881 -4.2283 -4.7098 -4.9045 -2.7139 -2.0928 -2.7012 -3.7819 Y 0 0.3114 0.5585 -0.1238 0.7365 -0.0647 -0.6355 -1.7036 -0.4444 -1.3881 0.1366 0.3618 0.8694 1.2959 1.3944 Z 0 -0.3078 -3.2261 0.4311 -1.6329 -1.2185 1.5116 1.6374 0.9229 0.6432 1.5582 -0.4814 -1.7267 -2.8867 -2.9722 122 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 -1.8742 -0.4838 0.1883 0.0106 1.3844 3.525 4.3157 3.8513 3.0081 3.5112 -2.5341 -1.4498 -2.8741 -3.9596 -2.407 -2.5188 -3.2581 -2.9577 -4.3501 -3.031 3.1559 2.7721 4.6332 5.0738 4.7547 5.2186 2.3252 2.4324 2.645 1.2571 0.6259 1.5264 1.9206 1.9682 2.6749 1.4992 1.9272 0.5966 0.2462 0.1648 -0.5421 0.4285 1.8363 1.5707 1.3574 1.4919 0.9232 0.4772 -0.0541 0.7014 -0.8857 -0.4954 0.0719 0.0648 -0.0438 1.5529 1.7221 2.07 2.0382 -0.6658 -1.7221 -0.6293 -0.2022 -1.9914 -2.1159 -2.3828 -2.3117 -3.4211 -1.7389 -2.8744 -3.9302 -2.7837 -2.6214 -1.1117 -0.8433 0.162 -1.8513 -1.6458 -3.144 -4.1213 -3.4562 -4.4831 -2.4312 -2.6875 2.0277 2.092 -4.0013 -3.9101 -4.7538 -2.6898 -2.3606 -2.5799 -2.5335 -3.2148 -1.1869 -0.3934 2.849 3.0098 2.826 2.7686 1.9775 3.745 3.9785 4.0275 3.8431 4.9479 -0.8717 0.1511 -0.8714 -1.8775 -0.5342 -0.1995 -1.7982 -1.5143 -2.8479 -1.7432 1.3993 2.4353 2.5794 3.2974 4.1028 3.1134 3.9365 2.1062 1.9932 1.2615 0.4668 1.0159 1.0557 123 H59 C60 C61 Si62 H63 H64 C65 H66 H67 H68 C69 C70 H71 H72 H73 H74 H75 H76 O77 C78 H79 H80 H81 H82 -0.031 -0.3144 3.0631 4.8852 -1.3821 0.1033 5.3338 6.4034 4.7551 5.133 5.8455 5.1909 4.8511 4.651 6.2638 5.5559 5.6891 6.9225 -2.4935 -1.7391 -2.4602 -0.997 -1.2379 -0.2414 1.6994 3.0896 2.1375 2.0723 2.8567 3.2348 3.5646 3.5415 3.5784 4.4998 2.0846 0.4761 -0.3946 0.4763 0.3507 2.9353 1.1575 2.1673 1.9832 2.2277 2.5514 3.0207 1.3099 4.0543 1.9529 0.246 1.1229 1.4734 0.1526 -0.7588 2.515 2.7733 3.4499 1.9722 -0.1384 2.4119 1.8323 3.3703 2.6222 -0.7724 -0.7077 0.0724 -5.0967 -6.2823 -7.0378 -6.1155 -6.62 0.7751 (S)-Transition State Calculated geometry Atom X Y Z 124 Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 0 -3.32 1.2099 -1.376 -1.1766 1.1664 -1.6222 -0.7951 -2.934 -2.8009 -3.7588 -2.3518 -2.3042 -3.1743 -4.0908 -2.838 -1.6144 -1.2858 -0.8117 0.5628 2.5126 2.5567 3.276 2.545 2.7385 -1.6575 -0.7229 -2.8305 -2.7076 -3.7877 -2.9108 -1.6287 -0.7419 -2.5211 -1.6102 3.5613 3.4163 4.9875 5.1642 5.2047 5.7128 3.306 3.4096 0 -1.3037 3.8325 -1.232 1.2945 1.6259 -2.6753 -3.0934 -2.7044 -3.0985 -3.2308 -0.6051 0.8728 1.7466 1.4108 3.1196 3.5435 4.5794 2.5669 2.6888 3.5376 4.0479 3.951 1.9938 1.6935 -3.4108 -3.1223 -2.9938 -3.4061 -3.3731 -1.903 -4.9207 -5.2213 -5.2577 -5.4587 1.2779 0.2048 1.6418 1.4354 2.7055 1.0574 1.5306 2.5956 0 -1.8934 -0.314 -0.791 -0.8375 0.0424 -0.9407 -1.53 -1.7652 -2.7784 -1.2738 -1.3415 -1.4088 -2.0217 -2.5037 -2.0171 -1.4613 -1.4835 -0.892 -0.351 0.2736 1.2419 -0.3941 0.3941 1.4324 0.4057 0.9112 1.289 2.2998 0.9007 1.3793 0.1744 -0.4018 -0.3758 1.1318 -0.5114 -0.3184 -0.1024 0.9629 -0.2832 -0.6845 -1.9953 -2.2544 125 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 H66 H67 H68 C69 C70 H71 H72 H73 H74 H75 H76 O77 C78 H79 H80 H81 H82 2.3007 4.0319 1.2855 1.8713 1.5399 2.8963 3.3536 3.3374 4.3232 2.7869 3.159 1.7627 1.3385 -0.9032 -2.252 -0.7301 -0.0784 -3.4221 -5.2359 -0.2398 0.9928 -5.899 -6.9818 -5.733 -5.4158 -5.4894 -6.0568 -7.1425 -5.6582 -5.8879 -6.5656 -5.0922 -5.0049 -3.7266 -3.4632 -4.3317 -3.3485 -2.5608 -0.3617 1.202 0.9761 -1.3002 -1.5584 -1.0289 -2.4984 -2.703 -3.1851 -4.0934 -2.9632 -3.5217 -2.0219 -1.8491 0.2311 0.5482 -0.8178 1.2509 0.832 1.1414 2.2635 1.0246 -0.1735 -0.0388 -1.1767 -0.1367 2.8657 0.9994 1.156 1.7502 0.0032 3.0945 2.9725 3.6189 3.934 5.335 5.7923 5.7378 5.5437 1.2595 -2.2952 -2.6053 0.4862 1.7294 2.6239 1.8742 2.8432 0.7524 0.8841 -0.5025 -1.3626 -0.6206 -1.6139 2.1006 1.8321 2.3569 2.8445 1.5849 1.3396 2.4532 2.7938 0.1778 0.0341 0.5978 -0.8078 0.6437 3.0202 2.9314 3.7181 3.4547 0.6081 -0.3745 1.2825 -2.5697 -2.6103 -3.092 -1.5945 -3.2015 3.9101 126 NMe2 L7 + E1 TMS Br O n-Bu O N N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 Atom X 0 -4.0028 2.3586 -1.945 -0.7593 1.5886 -2.8029 -2.6161 -4.2223 -4.7294 -4.8779 -2.7016 -2.0779 -2.6926 -3.7736 -1.8789 -0.4798 0.1942 0.0105 Y 0 0.4546 0.5767 -0.067 0.796 -0.0679 -0.5485 -1.6225 -0.3132 -1.241 0.2743 0.4577 0.9704 1.4511 1.5553 1.7628 1.483 1.6142 0.9971 Z 0 -0.2419 -3.2264 0.4576 -1.5937 -1.2273 1.5504 1.6795 0.9792 0.691 1.6298 -0.4387 -1.6811 -2.814 -2.8325 -3.9488 -3.8524 -4.6939 -2.6614 127 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 1.3734 3.4978 4.3114 3.7946 2.9798 3.5052 -2.4885 -1.4045 -2.7932 -3.8755 -2.3383 -2.4008 -3.2108 -2.9338 -4.3038 -2.9587 3.0888 2.7066 4.5546 4.9939 4.6495 5.1591 2.2293 2.3087 2.5456 1.1689 0.6189 1.572 2.0109 2.0115 2.759 1.4864 1.9111 0.5313 0.1379 0.104 -0.6441 0.4867 1.8923 0.0442 -0.278 3.1217 4.949 0.5041 -0.0822 0.648 -0.9102 -0.5373 -0.001 0.1502 0.0154 1.6461 1.8407 2.1471 2.1287 -0.5568 -1.6194 -0.4963 -0.0925 -2.0434 -2.1804 -2.4747 -2.3909 -3.5237 -1.8629 -2.8829 -3.9472 -2.7784 -2.6014 -1.1511 -0.921 0.0683 -1.9458 -1.7685 -3.2195 -4.2143 -3.4954 -4.5082 -2.4532 -2.6818 2.0199 2.0724 1.6623 3.0997 2.1048 2.0159 -2.3566 -2.603 -2.5484 -3.257 -1.215 -0.4142 2.8804 3.0231 2.8572 2.8288 1.993 3.7625 4.0257 4.0769 3.9065 4.9885 -0.9334 0.0881 -0.9489 -1.9547 -0.6371 -0.2639 -1.8741 -1.6137 -2.9236 -1.807 1.3735 2.3723 2.4987 3.2157 3.9905 3.0518 3.8564 2.0833 1.9852 1.2573 0.4923 1.0641 1.0697 1.9989 0.3392 1.1068 1.4181 128 H63 H64 C65 C66 C67 H68 H69 H70 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 N87 C88 H89 H90 H91 C92 H93 H94 H95 -1.3169 0.1577 -0.3001 5.4356 -1.1211 0.7333 -0.7114 -0.7041 -1.1699 -2.1453 -1.7657 -0.1601 -1.6161 6.5104 4.8778 5.2314 5.8794 5.2581 4.9001 4.7367 6.3337 5.5851 5.7052 6.9607 -2.4158 -1.5722 -2.1851 -0.7749 -1.1077 -3.8502 -4.081 -4.419 -4.1863 2.7795 3.2671 4.4202 3.4951 5.4995 4.7721 4.2376 5.6744 6.811 5.1234 7.5703 7.2217 6.6657 3.4601 3.5067 4.4365 2.0307 0.4097 -0.4539 0.4075 0.2736 2.8876 1.1085 2.1037 2.263 2.528 2.9573 3.2446 1.6056 2.4979 2.9437 1.5606 3.1909 0.1801 -0.6574 1.1173 2.4619 0.418 1.2674 2.1238 -0.5874 1.1933 0.2579 0.6678 1.3417 2.1885 2.6963 3.4095 1.9312 -0.2111 2.3388 1.7594 3.3074 2.5277 -0.8345 -0.7831 -0.0195 -5.0759 -6.2326 -7.0296 -5.9873 -6.6125 -5.1608 -6.1319 -5.0663 -4.3761 129 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 Atom X 0 -3.2354 1.1454 -1.3344 -1.174 1.1291 -1.5547 -0.6978 -2.8291 -2.6444 -3.6637 -2.2974 -2.267 -3.1239 -3.986 -2.8356 -1.6188 -1.2891 -0.8325 0.5187 2.4222 2.4009 3.2092 2.489 2.6655 -1.6389 -0.7305 Y 0 -1.3835 3.8524 -1.2627 1.2582 1.6493 -2.7111 -3.1305 -2.7746 -3.1775 -3.3124 -0.6588 0.8186 1.6561 1.2412 3.0556 3.4865 4.5208 2.5424 2.6965 3.5886 4.0909 4.0277 2.0466 1.745 -3.4189 -3.1074 Z 0 -1.9766 -0.3104 -0.8059 -0.8751 0.0661 -0.9364 -1.4805 -1.8154 -2.8171 -1.3539 -1.4036 -1.494 -2.1698 -2.6836 -2.1832 -1.5691 -1.6047 -0.9478 -0.3604 0.3425 1.3162 -0.2797 0.4551 1.496 0.4226 0.9613 130 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 C66 C67 H68 H69 H70 -2.8539 -2.7731 -3.7895 -2.9466 -1.5818 -0.668 -2.4462 -1.5967 3.5435 3.4069 4.9505 5.0968 5.1556 5.7033 3.3326 3.4349 2.3402 4.0822 1.2927 1.832 1.4656 2.8516 3.2699 3.3374 4.3178 2.8372 3.2438 1.8174 1.4323 -0.9741 -2.3118 -0.7957 -0.1455 -3.4751 -5.2693 -0.3451 0.9217 -0.4141 -5.8847 0.4542 -0.2326 -1.4796 1.5152 -2.9981 -3.3918 -3.3925 -1.9067 -4.9327 -5.2334 -5.293 -5.4505 1.3611 0.2828 1.7375 1.511 2.8083 1.1774 1.6379 2.7082 1.3063 1.1006 -1.2799 -1.5248 -0.9866 -2.4613 -2.6538 -3.1611 -4.0676 -2.9539 -3.5216 -2.0151 -1.8562 0.2265 0.5428 -0.8235 1.2452 0.8282 1.1585 2.2498 1.0464 1.2371 -0.1097 2.2411 0.2231 1.4515 2.0225 1.2452 2.2677 0.8209 1.3132 0.2256 -0.3068 -0.3539 1.1942 -0.4297 -0.2603 0.0311 1.097 -0.1197 -0.5399 -1.9164 -2.1532 -2.2538 -2.513 0.5377 1.8055 2.6812 2.0028 2.9918 0.9082 1.0899 -0.3699 -1.2081 -0.5392 -1.5507 2.0983 1.7983 2.3481 2.8416 1.5189 1.1909 2.44 2.6769 4.35 -0.0472 5.1029 4.7434 4.5327 4.8967 131 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 N87 C88 H89 H90 H91 C92 H93 H94 H95 0.2106 0.2707 0.8495 0.4193 -0.8359 -6.9551 -5.7602 -5.3448 -5.4581 -6.1886 -7.2655 -5.8225 -6.0578 -6.5196 -4.9069 -5.0858 -3.6708 -3.342 -4.1648 -3.2033 -2.425 -4.8616 -5.4212 -4.6027 -5.5169 2.2369 3.2499 2.9676 1.2468 2.4841 0.0482 -1.1271 -0.0559 2.9095 0.9686 1.1436 1.688 -0.0449 3.1304 3.0644 3.6364 3.9316 5.3493 5.8966 5.7409 5.5424 3.456 4.3164 2.8098 2.892 6.6075 4.6975 7.1228 7.0397 6.8405 -0.2488 0.3526 -1.0018 0.5429 2.8152 2.6696 3.5621 3.2218 0.3534 -0.3941 1.2797 -2.7732 -2.799 -3.2664 -1.7813 -3.3763 -3.4634 -3.8397 -4.3158 -2.7843 132 L8 + E2 NMe2 TMS Br O Me O N N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 Atom X 0 -4.01 2.3358 -1.9472 -0.7702 1.5818 -2.801 -2.6075 -4.2234 -4.734 -4.8742 -2.7085 -2.091 -2.716 -3.7983 -1.9117 -0.5102 0.1576 -0.0093 Y 0 0.4216 0.5883 -0.0826 0.8057 -0.0658 -0.5948 -1.6709 -0.354 -1.2789 0.2304 0.4427 0.9661 1.4304 1.5208 1.7387 1.4702 1.5945 1 Z 0 -0.2356 -3.2454 0.4622 -1.5867 -1.2433 1.544 1.6448 0.9815 0.6906 1.6399 -0.4294 -1.6703 -2.8046 -2.8191 -3.9467 -3.8554 -4.7029 -2.6625 133 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 1.3572 3.4852 4.2854 3.7983 2.9728 3.502 -2.4888 -1.4062 -2.785 -3.8657 -2.3137 -2.4038 -3.2203 -2.9519 -4.3124 -2.9675 3.0813 2.6971 4.5473 4.9886 4.6419 5.15 2.224 2.3028 2.5431 1.1635 0.6204 1.559 1.9894 1.9949 2.7316 1.4806 1.9026 0.5385 0.1527 0.1143 -0.6235 0.5042 1.9134 0.0476 -0.2188 3.142 4.9671 0.5103 -0.0577 0.6866 -0.8728 -0.5357 -0.0133 0.0688 -0.0749 1.5664 1.7684 2.0876 2.0212 -0.6636 -1.7294 -0.5912 -0.2279 -2.0461 -2.1986 -2.4768 -2.3768 -3.5305 -1.8756 -2.8709 -3.9392 -2.7499 -2.5907 -1.1771 -0.9744 0.0128 -2.0251 -1.8697 -3.2957 -4.315 -3.5443 -4.5555 -2.4771 -2.684 1.9899 2.0152 1.6462 3.0918 2.0284 1.9146 -2.3685 -2.627 -2.5621 -3.2894 -1.2447 -0.4374 2.892 3.036 2.9052 2.866 2.0616 3.8294 4.0155 4.0386 3.8951 4.9916 -0.9868 0.0318 -1.0061 -2.0095 -0.7108 -0.3103 -1.9423 -1.6984 -2.9892 -1.8735 1.35 2.3676 2.5332 3.1807 3.9703 2.9667 3.7414 1.9783 1.8409 1.1833 0.4022 1.0696 1.092 2.0024 0.338 1.1408 1.4568 134 H63 H64 C65 H66 H67 H68 C69 C70 H71 H72 H73 H74 H75 H76 N77 C78 H79 H80 H81 C82 H83 H84 H85 H86 -1.2928 0.1903 5.4689 6.5421 4.9074 5.2791 5.9011 5.2555 4.8903 4.7301 6.3288 5.618 5.7173 6.9828 -2.4593 -1.6252 -2.2463 -0.8309 -1.1574 -3.8966 -4.1367 -4.4545 -4.2369 -0.1139 2.8881 3.2503 3.3762 3.3247 3.3849 4.3258 1.9368 0.2945 -0.5579 0.2861 0.1444 2.8041 1.0232 1.995 2.2219 2.4784 2.8944 3.2028 1.5545 2.44 2.876 1.4972 3.1351 4.0404 0.2504 -0.6683 2.5182 2.7564 3.4637 1.9969 -0.1706 2.3597 1.7683 3.3261 2.5512 -0.7847 -0.7535 0.0237 -5.076 -6.2416 -7.0393 -6.0102 -6.6138 -5.1564 -6.1297 -5.0522 -4.3754 0.8904 (S)-Transition State Calculated geometry Atom X Y Z 135 Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 0 -3.2398 1.1703 -1.3402 -1.17 1.1393 -1.5627 -0.7114 -2.8462 -2.6765 -3.6818 -2.3 -2.2638 -3.1157 -3.9789 -2.8204 -1.6 -1.2627 -0.82 0.5345 2.4516 2.4472 3.2355 2.5048 2.6836 -1.6314 -0.7152 -2.8341 -2.7405 -3.7765 -2.9228 -1.581 -0.6756 -2.4544 -1.5838 3.5488 3.409 4.9617 5.1164 5.172 5.7061 3.3259 3.429 0 -1.3471 3.849 -1.2505 1.273 1.6455 -2.6961 -3.1036 -2.7426 -3.1439 -3.2733 -0.6345 0.8437 1.6904 1.2833 3.0885 3.5078 4.5398 2.5552 2.6979 3.5743 4.0802 4.0036 2.0316 1.73 -3.4333 -3.1359 -3.0277 -3.444 -3.4105 -1.9378 -4.9426 -5.2338 -5.2882 -5.4814 1.336 0.2593 1.7079 1.4887 2.7762 1.1389 1.6049 2.6735 0 -2.0005 -0.2996 -0.8252 -0.863 0.0745 -0.9823 -1.5443 -1.8493 -2.8542 -1.3809 -1.4153 -1.4879 -2.1584 -2.6767 -2.1612 -1.5462 -1.5774 -0.9298 -0.3469 0.3396 1.3115 -0.2934 0.4556 1.4961 0.3616 0.895 1.2096 2.222 0.7897 1.302 0.1307 -0.4208 -0.4444 1.0879 -0.4342 -0.2578 0.0116 1.0778 -0.1495 -0.5617 -1.9206 -2.1647 136 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 H66 H67 H68 C69 C70 H71 H72 H73 H74 H75 H76 N77 C78 H79 H80 H81 C82 H83 H84 H85 H86 2.3299 4.069 1.2924 1.8482 1.4921 2.8721 3.3041 3.3445 4.3288 2.8271 3.2234 1.8036 1.4053 -0.9511 -2.2943 -0.7691 -0.1478 -3.4597 -5.2554 -0.3125 0.9261 -5.8738 -6.9456 -5.7454 -5.339 -5.4462 -6.1711 -7.2485 -5.8043 -6.0382 -6.5078 -4.8953 -5.0738 -3.6515 -3.3144 -4.1354 -3.1705 -2.398 -4.8463 -5.4025 -4.5929 -5.5028 -0.4463 1.2741 1.062 -1.2898 -1.5549 -1.0322 -2.4927 -2.7014 -3.1724 -4.0799 -2.9442 -3.4966 -2.0048 -1.8284 0.2077 0.5129 -0.8416 1.232 0.7909 1.122 2.2441 1.016 -0.1307 0.0279 -1.1534 -0.0625 2.8805 0.9122 1.0874 1.6233 -0.1058 3.1031 3.0461 3.5992 3.9731 5.3891 5.9443 5.7732 5.5804 3.5089 4.375 2.868 2.9431 1.2347 -2.2476 -2.5204 0.5091 1.7653 2.6544 1.9326 2.9123 0.8195 0.9724 -0.4482 -1.3014 -0.5876 -1.5911 2.097 1.7956 2.3451 2.8568 1.5211 1.2007 2.4656 2.8205 -0.0516 -0.2453 0.3333 -1.0081 0.5736 2.8245 2.6833 3.579 3.2191 0.3872 -0.3617 1.3185 -2.7438 -2.7614 -3.2229 -1.7416 -3.3401 -3.4348 -3.8031 -4.2927 -2.7583 3.9184 137 L8 + E1 Me O N TMS Br n-Bu O N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 Atom X 0 -4.0037 2.3437 -1.9414 -0.7753 1.5804 -2.7932 -2.6038 -4.2159 -4.7223 -4.8696 -2.7045 -2.0916 -2.6997 -3.7807 Y 0 0.444 0.5675 -0.0774 0.7824 -0.0808 -0.5613 -1.6351 -0.3277 -1.2556 0.2571 0.4479 0.9603 1.4503 1.5816 Z 0 -0.2207 -3.2355 0.4665 -1.6072 -1.2347 1.564 1.6901 1.0002 0.7112 1.655 -0.4234 -1.6705 -2.8152 -2.8535 138 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 -1.8931 -0.5149 0.1355 0.0006 1.3634 3.4817 4.3052 3.7588 2.9733 3.5012 -2.4734 -1.3884 -2.7829 -3.8659 -2.3337 -2.3876 -3.1881 -2.9072 -4.2817 -2.933 3.0897 2.7204 4.5567 4.9831 4.6585 5.1678 2.222 2.3077 2.5259 1.1616 0.6308 1.5872 2.0218 2.0346 2.7845 1.5141 1.9463 0.5563 0.1672 0.1202 -0.6299 0.4776 1.8838 1.7431 1.4831 1.6421 0.9869 0.4937 -0.1042 0.6152 -0.939 -0.5467 0.0005 0.1362 0.0043 1.6311 1.8225 2.1359 2.1128 -0.5756 -1.6373 -0.5186 -0.1121 -2.0492 -2.176 -2.476 -2.4038 -3.5208 -1.854 -2.902 -3.9628 -2.8093 -2.623 -1.1335 -0.8886 0.1037 -1.9049 -1.7181 -3.1821 -4.1677 -3.4704 -4.4857 -2.4374 -2.6749 2.0146 2.0793 -3.9301 -3.8536 -4.713 -2.664 -2.362 -2.6218 -2.5802 -3.2758 -1.2261 -0.4342 2.8933 3.0305 2.8747 2.8519 2.0096 3.7792 4.0405 4.0885 3.9266 5.0029 -0.929 0.0986 -0.9572 -1.9693 -0.6335 -0.2873 -1.85 -1.5776 -2.9041 -1.7742 1.3779 2.3689 2.4849 3.2181 3.9882 3.0666 3.8774 2.1044 2.016 1.2716 0.5117 1.0403 1.0299 139 H59 C60 C61 Si62 H63 H64 C65 C66 C67 H68 H69 H70 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 C87 H88 H89 H90 0.0506 -0.3011 3.1129 4.9444 -1.3418 0.1204 -0.3183 5.421 -1.1544 0.7155 -0.7149 -0.7528 -1.1983 -2.179 -1.8058 -0.1886 -1.6291 6.4975 4.8692 5.2031 5.8608 5.2753 4.9221 4.7606 6.3534 5.5498 5.695 6.9425 -2.5028 -1.8548 -3.4862 -2.6497 1.6689 3.0883 2.1214 2.0547 2.7651 3.2536 4.4133 3.549 5.483 4.7709 4.2354 5.651 6.8008 5.1006 7.5522 7.2179 6.6622 3.5278 3.5636 4.4829 2.0637 0.4603 -0.4121 0.4619 0.3364 2.9093 1.1326 2.1536 2.3029 2.1397 1.8561 3.3871 1.9869 0.3201 1.0519 1.3491 0.1789 -0.6829 1.0904 2.3753 0.394 1.2233 2.1035 -0.6188 1.1585 0.2521 0.635 1.2882 2.1614 2.6028 3.3264 1.8368 -0.2878 2.2822 1.7132 3.2544 2.4648 -0.9185 -0.8477 -0.1059 -5.1806 -6.0492 -5.3722 -5.0643 140 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 Atom X 0 -3.2687 1.2475 -1.3624 -1.1539 1.1736 -1.601 -0.7734 -2.9161 -2.7998 -3.7512 -2.3166 -2.2562 -3.0844 -3.9761 -2.7327 -1.5346 -1.201 -0.7643 0.5912 2.5187 2.5101 3.3154 2.5457 2.7168 -1.6217 -0.6825 Y 0 -1.3387 3.8064 -1.2478 1.2783 1.6085 -2.6938 -3.1072 -2.7383 -3.1963 -3.2125 -0.6304 0.8443 1.7103 1.3362 3.0692 3.4885 4.5233 2.5444 2.6681 3.5147 4.0256 3.9285 1.9722 1.6745 -3.4284 -3.139 Z 0 -1.9461 -0.3703 -0.7804 -0.8942 0.0284 -0.9186 -1.5112 -1.7374 -2.725 -1.2106 -1.3781 -1.492 -2.1907 -2.6928 -2.2551 -1.6502 -1.7216 -0.9883 -0.406 0.2843 1.2535 -0.3425 0.4098 1.4527 0.4281 0.9238 141 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 C66 C67 H68 H69 H70 -2.7848 -2.6463 -3.7456 -2.8683 -1.593 -0.7122 -2.491 -1.5632 3.579 3.4189 4.9965 5.1421 5.227 5.7328 3.3669 3.4883 2.3672 4.1038 1.276 1.8475 1.5057 2.8721 3.3179 3.328 4.3134 2.7933 3.1778 1.7693 1.359 -0.9647 -2.3132 -0.7654 -0.1604 -3.4868 -5.3047 -0.3717 0.9117 -0.4469 -5.8938 0.3996 -0.2569 -1.5172 1.4657 -3.0139 -3.4226 -3.3981 -1.9232 -4.9382 -5.2373 -5.2764 -5.4767 1.2517 0.1789 1.6002 1.3832 2.6636 1.0148 1.5162 2.5816 1.1993 0.9582 -1.2803 -1.4604 -0.8766 -2.3871 -2.5307 -3.1402 -4.0367 -2.9962 -3.6045 -2.066 -1.9537 0.2816 0.5552 -0.7537 1.3437 0.7953 1.0305 2.3284 1.1555 1.3913 -0.3625 2.4355 0.396 1.5984 2.2218 1.3252 2.3355 0.9511 1.412 0.1955 -0.3905 -0.345 1.1524 -0.4723 -0.2896 -0.022 1.046 -0.1873 -0.5891 -1.961 -2.2103 -2.2909 -2.5545 0.5586 1.8224 2.6786 2.0373 3.0225 0.9651 1.1643 -0.3077 -1.1276 -0.4961 -1.5036 2.0795 1.7815 2.3718 2.7887 1.5034 1.2132 2.3455 2.6449 4.2932 0.1043 5.0155 4.7277 4.455 4.8313 142 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 C87 H88 H89 H90 0.1366 0.2094 0.7607 0.3507 -0.9154 -6.9753 -5.7074 -5.3786 -5.5882 -6.1567 -7.2441 -5.794 -5.9706 -6.6673 -5.1466 -5.1498 -3.6119 -3.0163 -4.2468 -4.2702 2.4877 3.425 3.2456 1.5179 2.7319 -0.2722 -1.3382 -0.3533 2.7017 0.9533 1.0743 1.7508 -0.0135 2.8947 2.7455 3.5091 4.0558 4.8356 3.5616 4.5503 6.5158 4.568 7.0097 6.9894 6.7257 -0.0784 0.5772 -0.866 0.4104 2.882 2.7625 3.5467 3.3719 0.3134 -0.5942 1.0151 -2.964 -3.4537 -3.7084 -2.2336 143 L9 + E2 CF3 TMS Br O Me O N N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 C18 H19 Atom X 0 -3.9378 2.7163 -1.9941 -0.5664 1.6625 -2.9959 -2.9093 -4.3327 -4.9647 -4.9178 -2.6256 -1.8548 -2.3118 -3.3694 -1.3573 -1.7735 -0.0105 0.7306 Y 0 0.6308 0.5584 -0.0118 0.8703 -0.1868 -0.5722 -1.666 -0.1153 -0.9459 0.561 0.5893 1.1319 1.7328 1.9423 2.028 2.7167 1.6911 1.8677 Z 0 -0.6371 -2.911 0.2673 -1.6442 -1.0851 1.1915 1.1369 0.5541 0.2239 1.1863 -0.6753 -1.8194 -2.9865 -3.136 -3.9615 -5.2459 -3.7903 -4.5688 144 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 H60 C61 C62 0.341 1.6279 3.7136 4.5926 3.9818 3.0127 3.4654 -2.7694 -1.7278 -2.9199 -3.9632 -2.3046 -2.6042 -3.6838 -3.5224 -4.7452 -3.495 3.0056 2.4952 4.4385 5.0074 4.4409 4.9772 2.2244 2.2117 2.6736 1.1811 0.5316 1.5329 2.0227 1.9537 2.7355 1.3628 1.7677 0.3655 -0.0738 -0.0426 -0.8181 0.4219 1.8152 0.1079 -0.4504 3.0208 1.0896 0.484 -0.2615 0.3654 -1.0771 -0.7406 -0.2702 -0.1625 -0.4436 1.3362 1.6679 1.9266 1.5852 -0.9795 -2.0586 -0.7673 -0.7363 -2.2617 -2.4212 -2.7735 -2.6543 -3.843 -2.2389 -3.0091 -4.0852 -2.8855 -2.6661 -1.1 -0.8352 0.1392 -1.811 -1.6119 -3.0661 -4.0127 -3.3722 -4.3706 -2.3801 -2.6329 2.0083 2.1521 1.6082 3.0899 2.3219 -2.5898 -2.1768 -2.2302 -2.0535 -2.9114 -0.9338 -0.0504 2.6523 2.8698 2.8955 2.7884 2.2056 3.9176 3.5644 3.4305 3.3621 4.6186 -0.7182 0.2417 -0.578 -1.5129 -0.328 0.2175 -1.7955 -1.5758 -2.7929 -1.8465 1.4387 2.3795 2.409 3.287 4.0213 3.2414 4.1095 2.3259 2.3192 1.4316 0.7038 1.0521 0.8836 2.0202 0.4638 0.7143 145 Si63 H64 H65 C66 H67 H68 H69 C70 C71 H72 H73 H74 H75 H76 H77 F78 F79 F80 H81 4.8308 -1.5082 -0.1309 5.2543 6.3173 5.0676 4.6527 5.1127 5.8253 5.6977 5.5387 6.8958 4.5841 4.748 6.1846 -1.1699 -3.0921 -1.4288 -0.3854 2.7061 2.8038 3.3695 4.0125 4.2881 3.6411 4.9205 3.3542 1.1471 0.3903 0.694 1.3975 4.3079 2.6489 3.5274 2.1605 2.647 4.0079 3.9952 0.5435 0.4352 -0.5484 1.8195 1.7449 2.8377 1.6685 -1.1945 0.8685 0.0822 1.8289 0.9173 -1.3394 -1.9548 -1.3731 -6.2997 -5.4363 -5.215 1.0894 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 Atom X 0 -3.3275 1.2529 -1.3829 -1.1774 Y 0 -1.275 3.8131 -1.223 1.3115 Z 0 -1.8927 -0.3072 -0.7886 -0.8293 146 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 C18 H19 C20 C21 C22 H23 H24 C25 H26 C27 H28 C29 H30 H31 H32 C33 H34 H35 H36 C37 H38 C39 H40 H41 H42 C43 H44 H45 H46 C47 C48 1.1821 -1.6285 -0.8195 -2.9676 -2.8803 -3.7864 -2.357 -2.2973 -3.1454 -4.0593 -2.7635 -3.6431 -1.5637 -1.2397 -0.7789 0.5935 2.5518 2.5985 3.3204 2.5665 2.7564 -1.6102 -0.6585 -2.7499 -2.5831 -3.7192 -2.8346 -1.5836 -0.7175 -2.4945 -1.5276 3.5741 3.4206 5.004 5.1799 5.2314 5.7226 3.3184 3.4287 2.3107 4.0398 1.2875 1.9035 1.6054 -2.6647 -3.0583 -2.6818 -3.1017 -3.1762 -0.5889 0.8886 1.7742 1.4263 3.1194 4.1072 3.5456 4.5836 2.5744 2.6784 3.4994 4.0035 3.9086 1.9545 1.6455 -3.4422 -3.1657 -3.0621 -3.5041 -3.4373 -1.9755 -4.9436 -5.2207 -5.267 -5.5122 1.2326 0.1602 1.5818 1.369 2.644 0.9925 1.4942 2.5596 1.1734 0.9376 -1.296 -1.5186 0.0398 -0.9658 -1.596 -1.7462 -2.7535 -1.2129 -1.3325 -1.4037 -2.0532 -2.5336 -2.0774 -2.8166 -1.5056 -1.5539 -0.8941 -0.3481 0.2816 1.253 -0.3824 0.3927 1.429 0.3567 0.8358 1.2979 2.2897 0.937 1.4237 0.0742 -0.5436 -0.4533 1.0123 -0.5181 -0.3293 -0.1093 0.9549 -0.2861 -0.6948 -2.0004 -2.2549 -2.3008 -2.6137 0.4758 1.7106 147 H49 C50 H51 C52 F53 C54 H55 C56 H57 C58 C59 H60 C61 C62 Si63 H64 H65 C66 H67 H68 H69 C70 C71 H72 H73 H74 H75 H76 H77 F78 F79 F80 H81 1.5894 2.9409 3.4239 3.3616 4.359 2.7794 3.1372 1.7435 1.2963 -0.8948 -2.2571 -0.6854 -0.1031 -3.4413 -5.2764 -0.2949 0.9745 -5.8879 -6.9813 -5.6439 -5.4404 -5.6227 -6.0515 -7.1453 -5.676 -5.8255 -6.7088 -5.2111 -5.1922 -3.3268 -3.5166 -4.9322 -0.3908 -0.9703 -2.4453 -2.6238 -3.1521 -4.0473 -2.9632 -3.5362 -2.0345 -1.8847 0.2196 0.4836 -0.8199 1.2737 0.7135 0.9293 2.2765 1.0792 -0.3592 -0.2885 -1.372 -0.2322 2.6682 0.6552 0.7615 1.3864 -0.3535 2.8392 2.8435 3.4142 5.3678 3.9488 3.9178 1.2854 2.5998 1.8503 2.8119 0.733 0.8604 -0.5131 -1.3695 -0.6277 -1.6142 2.0936 1.8352 2.3611 2.8256 1.6004 1.4038 2.4229 2.7816 0.1859 0.0819 0.5395 -0.809 0.7956 3.0891 3.0284 3.8197 3.4647 0.7464 -0.207 1.4795 -2.5203 -4.1379 -2.51 3.8899 148 t-Bu L10 + E1 TMS Br O n-Bu O N N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 C20 Atom X 0 -3.9994 2.3697 -1.9456 -0.758 1.5891 -2.8082 -2.6285 -4.2255 -4.7388 -4.8775 -2.6988 -2.0736 -2.6696 -3.7504 -1.8603 -0.4843 0.1899 0.0213 1.382 Y 0 0.4721 0.5824 -0.0664 0.7977 -0.0765 -0.5495 -1.6256 -0.3011 -1.2234 0.2878 0.4678 0.9788 1.4657 1.5947 1.7553 1.4952 1.6473 0.9998 0.505 Z 0 -0.2472 -3.2133 0.4523 -1.606 -1.2228 1.5414 1.6625 0.9701 0.6756 1.623 -0.4411 -1.682 -2.8319 -2.8616 -3.9491 -3.8539 -4.6928 -2.6578 -2.3485 149 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 3.5071 4.3153 3.8143 2.9785 3.5011 -2.4911 -1.4083 -2.7861 -3.867 -2.3269 -2.3918 -3.2204 -2.9505 -4.3127 -2.9671 3.0776 2.6845 4.5417 4.9929 4.6283 5.1406 2.2245 2.2965 2.5529 1.1646 0.6128 1.5693 2.0121 2.0065 2.7569 1.4755 1.8984 0.5163 0.1185 0.0905 -0.6603 0.4899 1.8966 0.0476 -0.2692 3.1257 4.9521 -1.3113 -0.0783 0.6563 -0.8966 -0.5515 -0.0291 0.1373 -0.0058 1.6353 1.8372 2.1405 2.1081 -0.574 -1.6387 -0.5052 -0.1187 -2.0622 -2.2122 -2.4995 -2.4007 -3.554 -1.902 -2.8837 -3.952 -2.7655 -2.5987 -1.1587 -0.9409 0.0452 -1.9773 -1.8119 -3.2469 -4.2521 -3.5084 -4.5184 -2.4558 -2.6721 1.9994 2.0497 1.6507 3.0853 2.0782 1.9886 2.7738 -2.5863 -2.5157 -3.2474 -1.2082 -0.3964 2.8769 3.0208 2.8648 2.8365 2.0052 3.7743 4.0151 4.0586 3.8943 4.9819 -0.9476 0.0679 -0.9538 -1.9528 -0.6587 -0.2514 -1.9097 -1.664 -2.954 -1.8501 1.3648 2.3619 2.4973 3.1921 3.9666 3.0151 3.8067 2.0466 1.9383 1.2333 0.4676 1.0643 1.0721 2.0028 0.3416 1.1125 1.4343 0.1859 150 H64 C65 C66 C67 H68 H69 H70 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 C87 C88 C89 C90 H91 H92 H93 H94 H95 H96 H97 H98 H99 0.1657 -0.2813 5.4312 -1.1024 0.7544 -0.6878 -0.6933 -1.1376 -2.1299 -1.7348 -0.1246 -1.5752 6.5043 4.867 5.2306 5.891 5.2535 4.9002 4.7251 6.3277 5.5965 5.7246 6.9709 -2.5067 -1.4712 -3.523 -3.2249 -1.9795 -0.7204 -0.9515 -3.9895 -3.0302 -4.3242 -3.6933 -4.0154 -2.5161 3.2522 4.4057 3.4703 5.4874 4.7532 4.2248 5.6569 6.8012 5.1161 7.5616 7.2076 6.6611 3.4357 3.4841 4.4104 1.9981 0.3839 -0.4804 0.3826 0.248 2.8495 1.071 2.0771 2.2939 2.5549 1.2564 3.6133 2.9525 3.2933 1.6341 1.6232 0.2991 1.0721 4.0164 3.4726 4.3613 -0.6555 1.1201 2.4775 0.4244 1.2639 2.1288 -0.5852 1.1961 0.2744 0.6738 1.3338 2.1959 2.7192 3.4213 1.9431 -0.1898 2.3595 1.7782 3.3242 2.5564 -0.8206 -0.7565 0.0074 -5.2249 -6.3224 -5.7351 -4.8909 -7.2106 -6.0082 -6.6218 -6.6598 -5.9562 -5.0069 -5.7992 -4.1413 -4.5087 151 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 Atom X 0 -3.2826 1.2367 -1.377 -1.181 1.1662 -1.5983 -0.7873 -2.9429 -2.8733 -3.7634 -2.3354 -2.2728 -3.0578 -3.9303 -2.672 -1.4981 -1.1173 -0.773 0.5802 2.5087 2.4962 3.3038 2.5437 2.734 -1.5511 -0.5947 Y 0 -1.2798 3.8212 -1.2214 1.3112 1.6168 -2.6618 -3.0226 -2.6848 -3.1425 -3.1472 -0.5875 0.8894 1.7563 1.371 3.1079 3.512 4.5273 2.5672 2.683 3.5206 4.0059 3.955 1.976 1.6534 -3.4776 -3.2048 Z 0 -1.9652 -0.2916 -0.7964 -0.821 0.0728 -1.0064 -1.6545 -1.7754 -2.7671 -1.2156 -1.3696 -1.451 -2.1933 -2.7187 -2.2999 -1.6449 -1.7194 -0.9288 -0.3398 0.3561 1.3385 -0.2587 0.4422 1.4742 0.2912 0.763 152 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 C66 C67 H68 H69 H70 -2.6783 -2.4899 -3.65 -2.771 -1.5138 -0.6566 -2.431 -1.4342 3.5668 3.4158 4.9893 5.1519 5.2129 5.7193 3.3306 3.444 2.3271 4.06 1.3193 1.9646 1.649 3.0357 3.5406 3.4635 4.4975 2.852 3.2149 1.7824 1.3145 -0.8728 -2.2326 -0.6359 -0.0606 -3.4215 -5.2468 -0.3103 1.0076 -0.2807 -5.8203 0.5784 -0.0538 -1.3463 1.6382 -3.1382 -3.6076 -3.5126 -2.0566 -4.9696 -5.2187 -5.2871 -5.5657 1.2847 0.2067 1.6275 1.38 2.6963 1.062 1.5886 2.6609 1.2765 1.0497 -1.2883 -1.5182 -0.9978 -2.4105 -2.5907 -3.0784 -3.9368 -2.8873 -3.4304 -1.9933 -1.8398 0.1384 0.3921 -0.9069 1.1794 0.6048 0.8214 2.1808 1.0221 1.1389 -0.4439 2.1579 0.1251 1.3148 1.9815 1.2624 2.2377 0.9071 1.4204 -0.0363 -0.6782 -0.5566 0.8828 -0.475 -0.3201 -0.0363 1.0226 -0.1738 -0.6311 -1.9524 -2.1746 -2.2752 -2.5722 0.4233 1.643 2.5488 1.7482 2.6982 0.6099 0.7021 -0.6215 -1.4952 -0.6998 -1.6762 2.1481 1.8994 2.367 2.8766 1.6666 1.4162 2.4951 2.6776 4.3928 0.156 5.1358 4.7624 4.6124 4.8876 153 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 C87 C88 C89 C90 H91 H92 H93 H94 H95 H96 H97 H98 H99 0.3895 0.3451 1.0199 0.6496 -0.656 -6.911 -5.5794 -5.347 -5.543 -6.0893 -7.1791 -5.7367 -5.8866 -6.614 -5.004 -5.1959 -3.4812 -2.8924 -3.46 -4.9301 -3.5117 -2.8763 -1.871 -4.0098 -2.4299 -3.9353 -5.5206 -5.4085 -4.973 2.1129 3.1677 2.8556 1.1223 2.3162 -0.3765 -1.4638 -0.2878 2.5668 0.5301 0.6465 1.2469 -0.4861 2.7402 2.7416 3.3065 4.0571 5.4709 3.505 4.124 6.1169 5.9101 5.4876 4.1873 3.4193 2.5171 4.7709 3.1354 4.545 6.6476 4.7597 7.1563 7.0497 6.9231 0.0251 0.4907 -0.8229 0.8042 3.0659 2.9645 3.8217 3.4346 0.6208 -0.1365 1.5404 -3.1859 -3.1915 -4.6235 -2.6766 -3.8276 -2.1843 -3.5964 -5.2863 -4.9975 -4.6916 -3.3398 -2.6611 -1.6629 154 L10 + E2 t-Bu TMS Br O Me O N N N i-Pr i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 Atom X 0 -4.0059 2.3477 -1.9471 -0.7689 1.582 -2.8055 -2.621 -4.226 -4.7452 -4.8712 -2.7052 -2.0867 -2.694 -3.7763 -1.8947 -0.5159 0.1517 0.0013 Y 0 0.4487 0.6163 -0.079 0.8183 -0.0648 -0.5957 -1.6744 -0.3368 -1.2539 0.2477 0.4609 0.9868 1.4605 1.5762 1.7487 1.5018 1.6509 1.0191 Z 0 -0.2345 -3.2273 0.4587 -1.5939 -1.2386 1.5356 1.6235 0.9759 0.6757 1.6395 -0.4267 -1.6647 -2.8144 -2.8391 -3.939 -3.8495 -4.6942 -2.6532 155 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 1.3659 3.4966 4.2862 3.8279 2.9712 3.4962 -2.4883 -1.4071 -2.7719 -3.8508 -2.2961 -2.3873 -3.2272 -2.9684 -4.3185 -2.9714 3.0679 2.6681 4.5319 4.9901 4.6167 5.1257 2.2209 2.2919 2.5555 1.1604 0.6132 1.5577 1.9942 1.991 2.7326 1.4684 1.8884 0.5197 0.1276 0.097 -0.6456 0.5138 1.924 0.0551 -0.2002 3.152 4.9758 0.5274 -0.0301 0.7228 -0.8274 -0.5406 -0.0416 0.0496 -0.1052 1.5494 1.7608 2.0777 1.9892 -0.69 -1.7583 -0.6063 -0.2684 -2.0578 -2.2343 -2.4952 -2.369 -3.5574 -1.917 -2.8527 -3.9275 -2.705 -2.57 -1.1942 -1.012 -0.0303 -2.0797 -1.9425 -3.3435 -4.3782 -3.5696 -4.576 -2.4867 -2.6749 1.9626 1.9842 1.6206 3.0774 1.9935 1.8658 -2.3567 -2.6059 -2.5151 -3.2806 -1.2401 -0.4157 2.8912 3.0347 2.9224 2.8855 2.0858 3.8525 4.0051 4.0155 3.8847 4.9865 -1.0198 -0.011 -1.0278 -2.0206 -0.761 -0.3053 -2.0092 -1.7933 -3.0477 -1.9481 1.333 2.3479 2.5279 3.1397 3.9281 2.9056 3.6595 1.918 1.7648 1.1442 0.3631 1.0832 1.1109 2.0157 0.3612 1.1668 1.4917 156 H63 H64 C65 H66 H67 H68 C69 C70 H71 H72 H73 H74 H75 H76 C77 C78 C79 C80 H81 H82 H83 H84 H85 H86 H87 H88 H89 H90 -1.2763 0.2116 5.4796 6.5511 4.9127 5.2987 5.9181 5.2474 4.8827 4.7144 6.3183 5.6401 5.7371 6.9987 -2.5548 -1.527 -3.5486 -3.3022 -2.0448 -0.7898 -0.9903 -4.026 -3.0345 -4.343 -3.7812 -4.0883 -2.6101 -0.0873 (S)-Transition State 2.8852 3.2444 3.3202 3.2613 3.3287 4.2729 1.8871 0.2399 -0.6076 0.2293 0.0833 2.7548 0.9733 1.9439 2.2628 2.5362 1.1977 3.5687 2.9178 3.291 1.6236 1.5455 0.25 1.0015 3.9514 3.4182 4.3369 4.0194 0.2723 -0.6428 2.5613 2.8056 3.5036 2.0425 -0.1307 2.3888 1.7901 3.351 2.5878 -0.7466 -0.7143 0.0701 -5.218 -6.3197 -5.7161 -4.8961 -7.2094 -6.012 -6.6143 -6.6426 -5.9303 -4.9836 -5.8078 -4.1439 -4.5234 0.9232 157 Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 H10 H11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 H22 H23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 Atom X 0 -3.3072 1.273 -1.3869 -1.165 1.1849 -1.6326 -0.8252 -2.9735 -2.8986 -3.7991 -2.3443 -2.2712 -3.0904 -3.9816 -2.7224 -1.5164 -1.1515 -0.7603 0.6042 2.5568 2.58 3.3416 2.5696 2.7625 -1.6089 -0.6513 -2.7372 -2.5653 -3.7127 -2.8116 -1.5954 -0.7381 -2.5143 -1.5328 3.5744 3.4149 Y 0 -1.279 3.8039 -1.2259 1.3021 1.6061 -2.6669 -3.0599 -2.6852 -3.1428 -3.1454 -0.5895 0.8864 1.7625 1.379 3.1152 3.5123 4.5357 2.5635 2.6723 3.4979 4.0094 3.9025 1.9549 1.6551 -3.4483 -3.1796 -3.0628 -3.5098 -3.4288 -1.9759 -4.949 -5.2304 -5.2649 -5.5211 1.2248 0.1538 Z 0 -1.9283 -0.3662 -0.7832 -0.8495 0.031 -0.9591 -1.5924 -1.7356 -2.7272 -1.1819 -1.3553 -1.4484 -2.1492 -2.6395 -2.2297 -1.6192 -1.689 -0.9516 -0.3888 0.2553 1.2239 -0.3924 0.3805 1.419 0.3605 0.8323 1.3132 2.3019 0.9595 1.4424 0.0739 -0.5544 -0.4445 1.0095 -0.527 -0.3353 158 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 H66 H67 H68 C69 C70 H71 H72 H73 H74 H75 H76 C77 H78 C79 C80 5.0062 5.1811 5.2393 5.7219 3.3208 3.4373 2.3113 4.039 1.2898 1.9144 1.6059 2.9527 3.4411 3.3674 4.3661 2.7782 3.1312 1.7417 1.2894 -0.8875 -2.2479 -0.6719 -0.0927 -3.4314 -5.2545 -0.2845 0.9845 -5.8608 -6.9489 -5.6482 -5.38 -5.5379 -6.0853 -7.1743 -5.7146 -5.8924 -6.6129 -5.0374 -5.1478 -3.5465 -0.3754 -3.8826 -2.7019 1.5672 1.3567 2.6277 0.9725 1.483 2.5471 1.1672 0.9203 -1.2972 -1.513 -0.958 -2.4387 -2.6102 -3.1536 -4.0482 -2.9734 -3.5524 -2.0453 -1.9028 0.2285 0.4877 -0.8088 1.2913 0.7136 0.9524 2.2881 1.0949 -0.3689 -0.2802 -1.3729 -0.2844 2.6673 0.7692 0.8957 1.5235 -0.2265 2.8503 2.7785 3.4416 4.1435 1.3188 5.323 4.6388 -0.1197 0.9452 -0.2995 -0.7033 -2.0104 -2.268 -2.3101 -2.6221 0.4773 1.7096 2.5969 1.8509 2.8112 0.7366 0.8649 -0.5073 -1.3617 -0.6223 -1.6076 2.1102 1.8448 2.3806 2.8251 1.602 1.3522 2.4079 2.7786 0.1676 0.0283 0.5638 -0.8165 0.65 3.0233 2.9258 3.7326 3.4486 0.5022 -0.3213 1.3265 -3.0051 3.8905 -2.0762 -4.1939 159 C81 H82 H83 H84 H85 H86 H87 H88 H89 H90 -4.8502 -4.4773 -4.469 -2.9797 -3.2783 -1.774 -2.4366 -5.4173 -4.6639 -5.4846 3.5432 6.0644 4.9896 5.8284 5.3733 5.125 3.807 4.3228 2.7307 3.1563 -3.54 -2.6273 -1.2091 -1.7085 -4.7733 -3.8635 -4.8615 -4.0654 -4.2558 -2.7304 160 L11 + E1 TMS Br n-Bu Me O Me O Me N N N i-Pr Me i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 C10 C11 C12 C13 C14 H15 C16 C17 H18 C19 Atom X 0 -4.0433 2.1554 -1.9563 -0.8637 1.5464 -2.817 -2.4872 -4.1991 -4.3469 -5.435 -2.7458 -2.1783 -2.8422 -3.9209 -2.0742 -0.701 -0.0904 -0.1365 Y 0 0.3498 0.4465 0.0551 0.6671 -0.1821 -0.3176 -1.2894 -0.5062 -1.9325 -0.0494 0.44 0.8594 1.3048 1.4523 1.5376 1.2813 1.4134 0.8236 Z 0 -0.1561 -3.4237 0.6026 -1.6318 -1.3587 1.7462 2.1325 1.0516 0.5402 1.7936 -0.3373 -1.6362 -2.7723 -2.7646 -3.917 -3.9151 -4.8068 -2.7297 161 C20 C21 C22 C23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 1.2444 3.4307 4.1558 4.1968 2.9293 3.5123 -2.7565 -3.6279 -1.5168 -0.5935 -1.4521 -1.5445 -2.874 -3.7252 -1.9684 -3.0001 3.0005 3.9196 1.8242 0.8918 1.9973 1.6658 3.1752 3.3518 2.289 4.0362 0.6333 1.6697 2.2266 2.0314 2.8396 1.3465 1.6934 0.311 -0.205 -0.0377 -0.8531 0.6519 2.0552 0.1567 -0.0285 3.2807 5.0859 0.36 0.0454 1.3351 -0.7698 -0.6857 -0.3219 0.6986 0.4647 0.489 0.6955 -0.547 1.1552 2.1518 2.3168 2.4728 2.8158 -2.2298 -2.4646 -2.861 -2.7456 -3.936 -2.4144 -2.8447 -3.926 -2.6977 -2.4053 -1.0275 -0.7841 0.1507 -1.7261 -1.5377 -2.932 -3.8468 -3.2196 -4.1783 -2.2576 -2.4954 2.1122 2.0932 1.891 3.129 2.0772 2.012 -2.4843 -2.7827 -2.4382 -3.8033 -1.4882 -0.6336 2.9002 3.53 3.7683 3.2137 4.1297 4.6414 2.4391 1.7652 1.9091 3.3046 -1.5195 -2.0734 -2.2649 -1.6933 -2.4084 -3.2573 -0.1323 -0.2212 0.4936 0.3903 1.4605 2.3669 2.3291 3.3332 4.0416 3.3836 4.31 2.5057 2.5727 1.5551 0.8658 0.8005 0.8665 1.7493 -0.0812 0.9733 1.4094 162 H63 H64 C65 C66 C67 H68 H69 H70 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 H87 H88 H89 H90 H91 H92 H93 H94 H95 H96 H97 H98 H99 -1.093 0.408 0.0739 5.212 -0.6725 1.1355 -0.329 -0.2756 -0.5793 -1.7304 -1.1283 0.4668 -0.997 6.2628 4.6486 4.8126 6.0181 5.7133 5.7341 5.0808 6.7384 5.6349 5.9304 7.0863 -2.5558 -4.4772 -5.2235 -3.4526 -5.5638 -5.3837 -6.3173 5.1269 4.3302 3.579 5.1539 3.6356 4.4106 2.8776 3.1112 4.551 2.4331 5.572 4.8339 4.5614 5.5406 6.9916 5.2705 7.7049 7.328 7.0527 2.4085 1.7092 3.4373 3.2616 0.2662 -0.0021 -0.4634 0.1731 4.2772 3.0439 3.2494 1.8954 -2.6117 -2.0165 -2.2485 -0.6582 1.0046 -0.1958 1.0945 1.9288 1.9299 -1.0982 -1.6504 -0.142 -0.1825 -1.0914 0.484 3.2329 -0.3697 0.5666 1.5102 -1.3977 0.1773 -0.4459 -0.4531 0.2301 1.1934 3.5596 3.84 3.4363 0.3704 1.1224 0.057 1.6493 1.5123 0.5473 -0.7032 0.6346 -4.827 1.3929 -0.1147 -0.0152 2.6975 2.0843 1.1572 -1.9867 -3.3447 -1.7185 -3.379 -4.1346 -4.6781 163 (S)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 C10 C11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 C22 C23 C24 H25 C26 Atom X 0 -3.2094 1.0227 -1.3932 -1.2259 1.1609 -1.634 -0.6936 -2.6053 -1.8181 -3.7266 -2.3358 -2.332 -3.2282 -4.1219 -2.9278 -1.7438 -1.4712 -0.9 0.472 2.3557 2.2427 3.3216 2.533 2.8219 -2.1229 Y 0 -1.4503 3.8965 -1.3246 1.2283 1.6893 -2.7775 -3.2568 -2.8084 -2.8569 -3.8233 -0.7275 0.7485 1.583 1.1794 2.9475 3.4336 4.4861 2.5112 2.7084 3.7301 4.269 4.5479 2.1684 1.8582 -3.4618 Z 0 -2.0029 -0.4348 -0.6975 -0.8802 -0.0717 -0.8477 -1.1453 -2.0674 -3.37 -2.0619 -1.3378 -1.4349 -2.091 -2.5639 -2.1304 -1.5698 -1.6268 -0.9621 -0.447 0.1938 1.6099 -0.6394 0.1955 1.2087 0.4404 164 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 C66 C67 H68 H69 -2.4863 -0.9803 -1.3365 -0.5782 -0.1483 -3.2708 -4.0795 -2.9195 -3.7027 3.5738 4.3429 2.9894 2.4576 2.2808 3.7905 4.2911 3.6082 4.7554 5.0883 1.2774 1.8801 1.5945 2.8633 3.3333 3.2485 4.1968 2.6827 3.0136 1.6994 1.2658 -0.9429 -2.2871 -0.7478 -0.0895 -3.4599 -5.2751 -0.3694 0.9669 -0.2251 -5.9973 0.652 0.0428 -1.2804 -4.4472 -3.7171 -4.3193 -2.7778 -4.2538 -2.7241 -2.457 -1.793 -3.3479 1.6005 2.3778 1.3473 2.225 0.5066 1.0967 0.3669 -0.4789 0.5795 0.0577 -1.2625 -1.3799 -0.7207 -2.3398 -2.4353 -3.1892 -4.1165 -3.1091 -3.7909 -2.1439 -2.0813 0.3712 0.6769 -0.667 1.4239 0.9589 1.2908 2.4145 1.2685 1.4134 -0.0181 2.4656 0.4125 1.5732 0.1102 1.4215 2.2686 1.8201 0.9447 1.126 0.4343 1.5859 1.9205 -0.7999 -0.897 -2.1895 -2.5852 -2.1724 -2.8976 -0.254 -0.1264 0.7197 -0.9448 0.5923 1.849 2.6703 2.1025 3.0823 1.0749 1.3112 -0.1897 -0.9743 -0.4152 -1.4171 2.123 1.8529 2.4041 2.7825 1.6103 1.3986 2.3951 2.5247 4.3088 0.2646 4.981 4.686 4.5832 165 H70 C71 H72 H73 H74 H75 H76 H77 H78 C79 C80 H81 H82 H83 H84 H85 H86 H87 H88 H89 H90 H91 H92 H93 H94 H95 H96 H97 H98 H99 1.6996 0.5501 0.3746 1.1898 0.8563 -0.4829 -7.052 -5.9576 -5.4624 -5.5023 -6.0617 -7.1464 -5.6369 -5.9006 -6.5741 -5.0922 -5.0077 -3.6108 -1.3572 -2.4819 -1.0171 -3.3029 -4.3625 -4.3491 3.2155 1.9527 1.5038 4.3328 3.3489 3.0096 2.3076 2.4474 3.4623 3.2149 1.4715 2.6322 0.2133 -1.0075 -0.0817 3.0088 1.1832 1.3567 1.9361 0.1897 3.2541 3.0844 3.7642 3.6358 -3.8475 -2.682 -2.1041 -4.8348 -3.7423 -3.6821 4.176 5.3275 3.7026 4.4853 4.2135 5.6001 4.6754 6.5017 4.6 6.9592 6.9073 6.8321 0.0515 0.7423 -0.6931 0.6826 3.0976 3.0284 3.7774 3.5408 0.6341 -0.3334 1.3105 -2.6284 -3.4781 -4.2262 -3.3773 -2.1004 -1.1752 -2.9548 2.1109 1.5973 2.189 -0.2186 -1.6826 -0.6176 166 L11 + E2 TMS Br Me Me O Me O Me N N N i-Pr Me i-Pr (R)-Transition State Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 C10 C11 C12 C13 C14 H15 C16 C17 H18 C19 Atom X 0 -4.0471 2.1368 -1.9584 -0.8698 1.5385 -2.8166 -2.4774 -4.1957 -4.3274 -5.4374 -2.7501 -2.1856 -2.8555 -3.9352 -2.0931 -0.7192 -0.1132 -0.1482 Y 0 0.3248 0.483 0.0295 0.6953 -0.1738 -0.3826 -1.3614 -0.5663 -1.9793 -0.1442 0.4316 0.8806 1.3334 1.4737 1.5799 1.3273 1.466 0.8617 Z 0 -0.1479 -3.433 0.6054 -1.617 -1.3738 1.737 2.097 1.0352 0.4838 1.7879 -0.325 -1.6156 -2.7453 -2.7327 -3.8907 -3.8967 -4.7905 -2.7175 167 C20 C21 C22 C23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 1.2324 3.4129 4.1604 4.1549 2.9165 3.5087 -2.7669 -3.6343 -1.5223 -0.6045 -1.4376 -1.5605 -2.9008 -3.7566 -1.9999 -3.0297 2.9774 3.8812 1.7803 0.8618 1.9437 1.6023 3.1822 3.337 2.318 4.0663 0.6359 1.658 2.2073 2.0149 2.8122 1.3388 1.681 0.3166 -0.1929 -0.0267 -0.8315 0.6508 2.0565 0.1542 -0.003 3.2812 5.0871 0.3888 0.0555 1.3296 -0.757 -0.6856 -0.3337 0.6022 0.3409 0.3856 0.6283 -0.6606 1.0217 2.0655 2.2397 2.408 2.7054 -2.2302 -2.4675 -2.8489 -2.7324 -3.9238 -2.3937 -2.854 -3.938 -2.6935 -2.4318 -1.0547 -0.8278 0.1122 -1.7939 -1.6188 -3.0057 -3.943 -3.2767 -4.2406 -2.2918 -2.5167 2.0861 2.0467 1.8629 3.1304 2.0194 1.9431 -2.4879 -2.8113 -2.4567 -3.8517 -1.5205 -0.6673 2.918 3.5425 3.7773 3.2283 4.1035 4.6722 2.4957 1.8299 1.9705 3.3788 -1.5653 -2.1426 -2.2874 -1.694 -2.4429 -3.2727 -0.1862 -0.2836 0.4664 0.3112 1.4397 2.3661 2.3625 3.3105 4.0344 3.3191 4.2244 2.4205 2.4546 1.4918 0.7858 0.8179 0.8824 1.7652 -0.0488 0.9863 1.4186 168 H63 H64 C65 H66 H67 H68 C69 C70 H71 H72 H73 H74 H75 H76 H77 H78 H79 H80 H81 H82 H83 H84 H85 H86 H87 H88 H89 H90 -1.0877 0.418 5.216 6.267 4.6523 4.8178 6.0209 5.7115 5.7287 5.0793 6.7375 5.641 5.9311 7.0895 -2.5798 -4.4511 -5.2024 -3.4293 -5.5604 -5.3982 -6.3173 5.1327 4.3335 3.5998 5.1123 3.5765 4.3666 0.1636 (S)-Transition State 2.9848 3.1472 2.3383 2.3082 1.6066 3.3399 3.2054 0.2011 -0.0508 -0.5353 0.1009 4.2196 3.0028 3.1865 1.943 -2.6835 -2.0545 -2.2699 -0.7797 0.9016 -0.2824 1.0684 1.9344 1.9215 -1.1047 -1.6251 -0.1212 4.1292 -0.1152 -1.0628 3.2477 3.5731 3.8452 3.4654 0.3961 1.1044 0.035 1.622 1.4899 0.5876 -0.6802 0.6585 -4.7959 1.3171 -0.1742 -0.0792 2.6741 2.1084 1.1465 -2.0192 -3.356 -1.7218 -3.4439 -4.1866 -4.7211 0.3878 169 Calculated geometry Ni1 O2 O3 N4 N5 N6 C7 H8 C9 C10 C11 C12 C13 C14 H15 C16 C17 H18 C19 C20 C21 C22 C23 C24 H25 C26 H27 C28 H29 H30 H31 C32 H33 H34 H35 C36 H37 C38 H39 Atom X 0 -3.2289 1.049 -1.4033 -1.2258 1.1732 -1.6488 -0.7119 -2.6314 -1.8563 -3.757 -2.3476 -2.3374 -3.2324 -4.1308 -2.9246 -1.7332 -1.4532 -0.8915 0.4879 2.3926 2.3153 3.3489 2.5536 2.8522 -2.1255 -2.4939 -0.9731 -1.3212 -0.5668 -0.1463 -3.2644 -4.0782 -2.9052 -3.6913 3.5755 4.3438 2.9661 2.4285 Y 0 -1.4089 3.8929 -1.3127 1.2443 1.6844 -2.7619 -3.2365 -2.768 -2.7976 -3.7781 -0.7011 0.776 1.6217 1.2274 2.9848 3.4583 4.5091 2.5254 2.7096 3.7146 4.2612 4.5184 2.1506 1.8411 -3.472 -4.4498 -3.7487 -4.3684 -2.8179 -4.2758 -2.7468 -2.4606 -1.8279 -3.3876 1.5687 2.3432 1.2999 2.1738 Z 0 -2.0098 -0.433 -0.7149 -0.8614 -0.0723 -0.8911 -1.2073 -2.1025 -3.4129 -2.1041 -1.3386 -1.4151 -2.0584 -2.5304 -2.0873 -1.5319 -1.5834 -0.9371 -0.437 0.1685 1.5839 -0.6892 0.1742 1.1847 0.3874 0.0408 1.3512 2.1892 1.7653 0.8549 1.1006 0.4228 1.5785 1.8842 -0.8334 -0.9546 -2.2092 -2.6056 170 H40 H41 C42 H43 H44 H45 C46 C47 H48 C49 H50 C51 F52 C53 H54 C55 H56 C57 C58 H59 C60 C61 Si62 H63 H64 C65 H66 H67 H68 C69 C70 H71 H72 H73 H74 H75 H76 H77 H78 H79 H80 H81 H82 2.2571 3.7543 4.3018 3.6201 4.7886 5.0825 1.2772 1.8922 1.6171 2.8745 3.3548 3.2457 4.1926 2.6673 2.9874 1.6855 1.2417 -0.9113 -2.2629 -0.7102 -0.0806 -3.4393 -5.2572 -0.3191 0.994 -5.9862 -7.0421 -5.9449 -5.4587 -5.4908 -6.0339 -7.1198 -5.6089 -5.8657 -6.5633 -5.0831 -4.9966 -3.6067 -1.4006 -2.527 -1.0522 -3.3383 -4.3841 0.4605 1.0401 0.3415 -0.5004 0.5681 0.0193 -1.2765 -1.4259 -0.7857 -2.395 -2.5158 -3.2207 -4.1568 -3.1078 -3.7714 -2.134 -2.0456 0.3515 0.6438 -0.6846 1.4153 0.9166 1.2461 2.4105 1.2366 -0.0361 0.2015 -1.0365 -0.0782 2.9799 1.0964 1.2661 1.8355 0.0937 3.2237 3.0803 3.7217 3.6816 -3.7881 -2.6052 -2.0481 -4.7907 -3.7103 -2.1702 -2.9285 -0.2849 -0.1288 0.6745 -0.9885 0.5592 1.8061 2.6457 2.0257 2.9977 0.9738 1.1779 -0.2827 -1.0871 -0.4743 -1.4698 2.1254 1.8603 2.4079 2.7918 1.6288 1.4339 2.3966 2.6695 0.2741 0.074 0.7281 -0.6887 0.7589 3.1342 3.0749 3.8288 3.5536 0.7187 -0.2559 1.4031 -2.5744 -3.5421 -4.2598 -3.4146 -2.1648 -1.21 171 H83 H84 H85 H86 H87 H88 H89 H90 -4.3874 3.297 2.0384 1.5806 4.3684 3.3504 3.0476 -0.2907 -3.6184 4.1583 5.3231 3.7057 4.4483 4.1781 5.5737 1.4307 -2.9884 2.0651 1.5723 2.1794 -0.2901 -1.731 -0.6668 3.8742 172 5. References (1) Markownikoff, W. I. Ueber Die Abhängigkeit Der Verschiedenen Vertretbarkeit Des Radicalwasserstoffs in Den Isomeren Buttersäuren. Justus Liebigs Ann. Chem. 1870, 153 (2), 228–259. https://doi.org/10.1002/jlac.18701530204. (2) Saytzeff, A. Zur Kenntniss Der Reihenfolge Der Analgerung Und Ausscheidung Der Jodwasserstoffelemente in Organischen Verbindungen. Justus Liebigs Ann. Chem. 1875, 179 (3), 296–301. https://doi.org/10.1002/jlac.18751790304. (3) XIV. Researches into the Molecular Constitution of the Organic Bases. Philos. Trans. R. Soc. Lond. 1851, 141, 357–398. https://doi.org/10.1098/rstl.1851.0017. (4) Walden, P. Ueber Die Gegenseitige Umwandlung Optischer Antipoden. Berichte Dtsch. Chem. Ges. 1896, 29 (1), 133–138. https://doi.org/10.1002/cber.18960290127. (5) Schrödinger, E. An Undulatory Theory of the Mechanics of Atoms and Molecules. Phys. Rev. 1926, 28 (6), 1049–1070. https://doi.org/10.1103/PhysRev.28.1049. (6) Hartree, D. R. 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My contributions to these works are collected here. 1. Enantio- and diastereoselective allenylation of alkyl electrophiles. 1.1 Background Stereochemically rich compounds are common in both natural products and pharmaceutical compounds of interest. In recent years, this has motivated the development of metal-catalyzed reactions to accomplish stereoselective and stereospecific couplings.1,2 Our group has been particularly interested in nickel-catalyzed asymmetric constructions of C—C bonds between alkyl coupling partners.3,4 When a racemic nucleophile and electrophile are used, there is the possibility of accomplishing controlling both chiral centers at once, swiftly adding synthetic complexity. These so-called doubly enantioconvergent couplings have been of interest in recent years, with examples published using nickel,5–9 cobalt,10,11 copper,12–14, and iridium,15 and others.16,17 Our group has made inroads into this motif as well first in 2017, when we reported the diastereoselective coupling of α-zincated pyrrolidines with secondary cyclic electrophiles.18 This was followed in 2020 by our report of the doubly enantioconvergent coupling of acyclic coupling partners, specifically secondary propargylic bromides and β-zincated amides.19 At the start of this project, it was noted that there had not yet been a report of a coupling reaction that simultaneously controlled axial and point chirality simultaneously . Therefore, we sought to fill this gap by exploring the hydroalkylation of enynes with secondary electrophiles via nickel hydride catalysis20 to generate synthetically valuable chiral allenes.21–24 After a period of optimization, a suitable 258 (A) CF3 R Br NiBr2•glyme (10 mol%) (12 mol%) L* (3.0 equiv.) TMS TMS HSi(OMe)3 CF3 K3PO4•H2O (3.0 equiv.) • Me ° R THF, 0 C Ar Ar 1.7 equiv. Me O Ph N L* N Cy CF3 (B) CF3 R TMS • R LNiI Br A Me R CF3 • L*BrNiIII Ar F Br (MeO)3Si H (MeO)3Si Br Ar P R Br CF3 R LNiII C Br L*BrNiII Br B H TMS TMS Ar Me O TMS L*BrNiII • Ar E Me L*BrNiII Ar TMS H D Figure 1.1.1: (A) Reported enantio- and diastereoselective hydroalkylation of enynes. (B) Proposed catalytic cycle consistent with observations. reaction condition was found using a chiral pyridine-oxazoline ligand to coupling αtrifluoromethyl bromides with enynes (Fig 1.1.1A)20. A proposed mechanistic cycle for this process which is consistent with mechanistic experiments and is analogous to previously studied mechanisms is shown in Figure 3.1.1.1B25,26. In the cycle, metalloradical A would undergo halogen atom abstraction with the alkyl halide Br to generate organoradical R and nickel species B. This species can undergo transmetalation with the silane reductant to form nickel hydride C, which can then undergo hydroalkylation with the enyne substrate O to form propargylic nickel intermediate D. This intermediate can rearrange to the more thermodynamically stable allenyl species E. This 259 species can then capture the radical R to form intermediate F, which undergoes rapid reductive elimination to form the product P and regenerate metalloradical A. In performing calculations on this system, there were two key questions that we hoped to shed light on. The first is the nature of the rearrangement step from species D to E. The second was to rationalize the differing reactivity of different electrophiles. Specifically, it was observed that alkyl iodides as well as unfluorinated secondary bromides displayed worse reactivity, and secondary unactivated alkyl iodides were completely unreactive, which is an unexpected result in light of the lower BDE of the C—I bond. 1.2: Calculations of NiII hydride species Me Me Ph O N Br rel. energy (kcal•mol-1) NiII "cis" 0.00 N H Ph Cy O N NiII N Cy H Br "trans" 1.59 Figure 1.2.1: Calculated relative energies of nickel hydride isomers. As a start to investigating the possible geometries of the nickel-alkyl intermediates, the putative NiII hydride species was calculated. Given the symmetry of the ligand, two possible low spin square planar isomers are possible. In the first, the hydrogen atom lies trans to the oxazoline fragment, and in the other it is trans. Figure 1.2.1 shows the geometry of these species, and their calculated energy differences. The cis geometry was found to be the most stable. However, the trans isomer is close enough in energy that it cannot be ruled out as a relevant species, given that interconversion may occur, and the trans isomer may be more reactive with the enyne. 260 1.3: Calculations of L*NiBr—propargyl species (A) TMS L*BrNiII hydroalkylation H Ar Me Ph NiII Br Me3Si (R) "trans" N Me Me Ph O N NiII O Ph Me3Si N NiII Me 1.1 (-7.7) Ph Me O N TMS H Ar "cis" (B) (S) L*BrNiII N Br Me 0.2 (-8.6) Ph Me SiMe3 Ph Ph Ph N Br 0.0 (-8.8) O NMe N NiII Br SiMe3 2.2 (-6.6) Figure 1.3.1: (A) Modeled hydroalkylation reaction. (B) Lowest-energy isomers for NiII propargyl species. Numbers are relative energy in kcal•mol-1. The bracketed values are energies relative to the starting materials. We next moved to interrogate the possible geometries of the NiII species after hydroalkylation with the enyne, a reaction shown in Figure 1.3.1A. Because we could not assume the geometry of the NiII—H species, complexes resulting from reaction of both the cis and trans isomers of the NiII hydride species were considered. An extensive geometric search was performed to find the lowest energy conformation of each diastereomeric complex. The result of this search is shown in Figure 1.3.1B, showing the four lowest energy isomers. It should be noted that the diastereomer with the R configuration on the propargyl group corresponds to the stereochemistry of the major project. Overall, the reaction is downhill for each isomer. This is consistent with the mechanistic data which shows that hydroalkylation is an irreversible process under the reaction 261 conditions. While we can note that, on average, the R conformers are more stable than the S conformers, the difference is not very great. Efforts were made to locate transition states for the hydroalkylation step, but they were not successful. With the present data, no concrete conclusions can be reached about the probable geometry of the NiII—propargyl species. 1.4 Calculations of L*NiBr—allenyl species We next turned our attention to the next step in the putative catalytic cycle: the rearrangement of the NiII-propargyl species to a NiII-allenyl species (Fig 1.4.1A). As before, an extensive geometry search was undertaken. Figure 1.4.1B shows the results. In this case, the relative energy of the diastereomers is very close, and no determination can be made about how (A) L*BrNiII TMS H TMS rearrangement Ar Me N Br (R) "trans" O Me3Si Ph NiII N • Me Me Me NiII NiII N 1.2 (-23.6) • N Br SiMe3 0.4 (-24.4) Me O Me Br N • Me N O Ph 0.0 (-24.8) Ph Me Ar "cis" (B) (S) • L*BrNiII SiMe3 Ph O N NiII • Me3Si Me N Br 0.0 (24.8) Figure 1.4.1: (A) Modeled rearrangement. (B) Lowest-energy isomers for NiII allenyl species. Numbers are relative energy in kcal•mol-1. The bracketed values are energies relative to the starting materials. 262 the relative energies of these structures effect the ultimate diastereoselectivity. What can be said is that the NiII-allenyl species is significantly downhill from the NiII-propargyl species, and therefore this step is likely irreversible. It also cannot be ruled out that these species may interconvert. Unfortunately, reasonable transition states for this rearrangement reaction were not located. The bond dissociation energy for dissociation of the allenyl fragment was calculated to be 10 kcal•mol1 . This places within the realm of possibility that under the reaction conditions, rearrangement of the allenyl species can take place by dissociation and reassociation of the allenyl radical. By extension, this could also be a reasonable pathway for isomerization of the propargyl species to the allenyl species. It should be noted that using α-bromo lactams as electrophiles results in the opposite sense of allene axial chirality. This is consistent with an interconverting NiII-allenyl species, where one diastereomer preferentially can capture the alkyl radical and undergo reductive elimination to the product. This would mean that radical capture would be both the enantio- and diastereo- determining step. 1.5: Estimation of bond dissociation energies X R Br NiBr2•glyme (10 mol%) (12 mol%) L* (3.0 equiv.) TMS TMS HSi(OMe)3 X K3PO4•H2O (3.0 equiv.) • Me ° R THF, 0 C Ar Ar R=CH2CH2(p-anisyl) 1.7 equiv. 1.0 equiv. additive Me Ph O N L* N entry X additive yield (%) ee (%) dr additive recovery (%) 1 X = CF3 -- 65% 92% 90:10 -- 2 X = CF2H -- 55% 71% 85:15 -- 3 X = Me -- No T.M -- -- -- 4 X = CF3 40% 88% 90:10 87% O I Figure 1.5.1: Results of catalysis using different electrophiles and with a secondary alkyl iodide as an additive. No T.M = no target molecule detected. Cy 263 Me Ph Me O N NiI N R1 Cy R2 X ∆Gabstraction O Ph N NiII N Br Br R1 R2 Substrate CF3 Br X ∆GBDFE R1 Cy R2 X R1 R2 X ∆Gabstraction ∆GBDFE -5.44 57.16 -3.84 58.78 -2.67 59.93 -2.26 44.89 MeO CF2H Br MeO CH3 Br MeO I O Figure 3.1.5.2: Free energies of halogen atom abstraction by LNiIBr and bond energy BDFE values calculated. All values are in kcal•mol-1 During our investigation, some unexpected reactivity was discovered regarding the identity and tolerance of the electrophile. These findings are summarized in Figure 3.1.5.1. Entries 1, 2, and 3 show the necessity of an α-fluorinated substituent on the catalysis. While changing the α-trilfuoromethyl group for an α-difluoromethyl group results in somewhat worse results, replacement of this group by methyl completely shuts down. This may be explained by a weakening of the C—Br bond as a result of an electronegative α-group. However, it was also noted that secondary unactivated alkyl iodides were tolerated in this reaction. These results encouraged us to calculate both the BDE energies of bond homolysis of the relevant carbon-halogen bonds, 264 but also calculate the favorability of halogen atom abstraction by the putative NiI—Br complex implicated in the catalysis. Figure 3.1.5.2 shows the results of these calculations. For each of the bromide substrates, halogen atom abstraction is favorable for each one, but it is most favorable for the α-trifluoromethyl substrate, and barely exergonic for the unfluorinated case. This effect can mostly be explained by the weakening of the C—Br bond as fluorination increases. Interestingly, the abstraction of an iodine atom from the tetrahydropyran substrate is the least exergonic, even though the C—I bond was calculated to be the weakest. This disparity can be attributed to the greater affinity of the nickel catalyst for bromine over iodine. 1.6: Computation details 1.6.1 General methods All molecular structure images were generated using the Mercury software package.27 Calculation method A: All calculations were performed using the Orca 5.0.3 software package. 28–31 Geometry optimizations were performed using the B3LYP functional, utilizing the D4 dispersion correction. 32–34 The def2-SVP basis set was used for all atoms except nickel where applicable, with which def2-QZVPPD was used.35,36 The RIJCOSX approximation was used with the def2/J auxiliary basis set in all calculations.37 Frequency calculations were performed to ensure that all molecular geometries were energy minima by confirming the absence of imaginary vibrational modes.38 Solvent was modeling using the CPCM solvation model with THF as a solvent.33,39 All thermochemical values were corrected to 273.15 K. Calculation method B: All calculations were performed using the Orca 5.0.3 software package.28–31 Geometry optimizations were performed using the B3LYP functional, utilizing the D4 dispersion correction.32–34 The def2-TZVP basis set was used for all atoms except nickel where 265 applicable, with which def2-QZVPPD was used.35,36 The RIJCOSX approximation was used with the def2/J auxiliary basis set in all calculations.37 Refinements to the electronic energy were calculated by single point calculations on optimized geometries using the MO62X functional using the def2-QZVPPD basis set.40 This functional was chosen on the basis of its previous success in predicting the thermochemistry of bond-breaking reactions.41 Frequency calculations were performed to ensure that all molecular geometries were energy minima by confirming the absence of imaginary vibrational modes.38 1.6.2 Geometry of calculated species These geometries were calculated using calculation method A. L*NiBr—H, cis Calculated geometry Ni1 O2 N3 N4 C5 H6 C7 H8 H9 C10 Atom X 0 1.0014 0.9739 -1.4156 2.3521 2.5683 2.2753 2.2341 3.0681 0.3547 Y 0 3.8116 1.6043 1.234 1.9863 1.65 3.5346 3.9976 4.0066 2.6571 Z 0 -0.2485 0.1242 -0.7883 0.4721 1.497 0.413 1.4089 -0.1801 -0.2915 266 C11 C12 H13 C14 C15 C16 H17 H18 C19 Br20 C21 C22 C23 C24 C25 C26 H27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37 C38 C39 C40 C41 C42 C43 H44 H45 H46 H47 H48 H49 H50 H51 -1.0029 -1.79 -1.3965 -3.077 -3.5086 -2.6303 1.1019 -2.9287 -3.9144 -1.2088 3.1506 3.368 4.8095 5.8326 5.6138 4.1785 3.2368 2.1301 3.2047 4.9518 4.9847 6.8562 5.7384 5.8116 6.3352 4.0138 4.0224 -7.3218 -7.2596 -6.0246 -4.8311 -4.9054 -6.1409 -8.2893 -8.1789 -5.9895 -3.9855 -6.1804 -4.5265 -4.6067 -3.2776 2.5217 3.5574 4.5753 3.2831 1.9377 0.9594 -0.753 -0.0911 4.4058 -1.9807 1.6943 1.329 1.6277 0.9402 1.3124 1.0051 2.7888 1.4159 0.241 1.3085 2.7196 1.2024 -0.1554 2.3925 0.779 -0.0876 1.3131 0.5817 1.641 2.0951 1.4919 0.4201 -0.0277 0.2305 2.1147 2.9088 -0.0546 -0.8551 4.0775 4.7867 5.2449 -0.81 -1.2886 -1.2935 -1.7799 -1.7565 -1.2506 0.5848 -1.2071 -2.3247 -0.1022 -1.9545 -0.4783 -0.0374 -0.9488 -2.4194 -2.86 -2.0855 -2.2652 -0.3765 1.0094 -0.0601 -0.632 -0.8343 -2.5539 -3.0613 -2.8256 -3.9076 -3.2063 -2.2947 -1.8273 -2.2616 -3.1697 -3.6421 -3.5745 -1.9408 -1.1005 -3.5202 -4.3552 -3.1768 -1.5556 -2.639 267 L*NiBr—H, trans Calculated geometry Ni1 O2 N3 N4 C5 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 H17 Br18 H19 C20 H21 C22 C23 C24 C25 Atom X 0 1.0083 1.087 -1.3395 2.4586 2.7342 2.3171 2.2953 3.0667 0.4143 -0.9623 -1.804 -1.4355 -3.1095 -3.5055 -2.5788 3.3548 1.5763 -2.8587 -4.0038 -0.9101 5.9187 4.9059 3.4626 3.166 Y 0 3.8467 1.6575 1.153 2.1132 1.8315 3.6537 4.1647 4.126 2.6613 2.4517 3.4354 4.4592 3.1083 1.7583 0.8284 0.3679 -1.3978 -0.2183 4.1782 -1.1415 1.1407 1.8383 1.4529 1.7262 Z 0 -0.4759 0.0054 -0.7533 0.275 1.3022 0.1465 1.1196 -0.5003 -0.431 -0.8714 -1.3629 -1.4463 -1.763 -1.6342 -1.1288 -0.5184 0.9805 -1.0125 -2.3221 -0.0559 -1.2443 -0.329 -0.6875 -2.1691 268 C26 C27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37 C38 C39 C40 C41 C42 C43 H44 H45 H46 H47 H48 H49 H50 H51 4.1817 5.6208 5.878 6.9425 5.0325 5.1063 2.1456 3.2012 4.0642 3.9686 5.7674 6.3354 -7.3778 -6.2172 -4.9616 -4.8484 -6.0212 -7.2755 -8.3605 -6.2881 -4.0583 -5.9533 -8.1778 -4.6615 -4.6535 -3.4061 1.0247 1.4134 0.0512 1.464 2.9334 1.5864 1.3907 2.8139 -0.0694 1.2617 2.4902 0.8702 0.2519 -0.3557 0.1407 1.2587 1.8605 1.3586 -0.1376 -1.2199 -0.333 2.712 1.8321 3.7846 4.5955 5.0059 -3.0792 -2.7229 -1.0613 -0.9909 -0.421 0.7266 -2.4178 -2.3657 -2.9722 -4.1353 -2.9302 -3.3643 -2.7373 -3.2266 -2.869 -2.0235 -1.5348 -1.8878 -3.0153 -3.8921 -3.2618 -0.855 -1.4924 -3.1099 -1.5348 -2.7295 269 L*NiBr—propargyl, (R), cis Calculated geometry Ni1 O2 N3 N4 C5 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 Br17 H18 C19 C20 Si21 C22 Atom X 0 -1.759 -1.2608 0.9546 -2.2994 -3.0776 -2.8438 -3.7283 -3.0461 -0.9835 0.203 0.5608 -0.0769 1.7464 2.5205 2.0735 2.0159 2.6516 -1.3245 -1.7321 -0.7267 -2.4708 Y 0 0.8286 0.6626 -0.6347 1.7124 1.514 1.5211 0.8677 2.4528 0.3445 -0.4513 -0.9416 -0.7367 -1.6795 -1.8949 -1.343 0.1114 -1.4749 -0.1145 1.2004 -1.0017 -0.9657 Z 0 -3.4914 -1.3115 -1.7089 -1.3691 -0.6208 -2.7996 -2.8362 -3.3405 -2.5306 -2.8161 -4.0629 -4.9244 -4.2068 -3.0436 -1.8277 1.2211 -0.911 1.4937 1.8711 3.1063 0.8928 270 C23 H24 H25 H26 C27 C28 C29 C30 C31 C32 H33 H34 H35 H36 H37 C38 C39 C40 C41 H42 H43 H44 H45 H46 H47 H48 H49 H50 C51 C52 C53 C54 C55 C56 H57 H58 H59 H60 H61 H62 H63 H64 H65 -2.0506 -3.2804 -2.9291 -2.1024 -2.9038 -3.9359 -3.6662 -2.348 -1.3162 -1.595 -3.119 -4.9617 -4.474 -0.2929 -0.7825 2.1469 0.1664 0.2456 -2.2967 0.2641 -0.4104 1.1694 0.4258 1.2111 -0.345 -2.0115 -2.9555 -2.8797 -0.5774 -1.687 -2.7858 -2.2125 -1.0934 -0.0005 -0.9767 0.2294 -1.2332 -3.5463 -3.3009 -3.0174 -1.8156 -1.5171 -0.6614 2.323 -1.1288 -0.5015 -1.958 6.3509 5.4978 4.1703 3.6649 4.5351 5.8608 7.3911 5.8717 3.5084 4.1567 6.519 -2.1765 -2.6236 0.1065 -1.4675 -3.2235 -3.219 -2.4491 -0.4427 0.4247 1.005 -1.8287 -0.5929 -2.2644 3.5177 3.0967 4.1683 5.541 5.9579 4.8861 3.5732 2.7664 3.0119 3.8654 4.2407 6.2953 5.4994 6.1144 6.9241 2.2466 1.6237 0.0102 0.587 3.2973 2.8882 2.5566 2.6215 3.0433 3.3757 3.5548 2.8266 2.2365 3.0981 3.6956 -5.5675 2.7243 4.285 4.0765 3.6452 1.9968 2.3102 5.2254 3.8717 4.5281 5.0797 4.2096 3.5878 -2.054 -1.0783 -1.0001 -0.6333 -1.5935 -1.6696 -3.0832 -2.0636 -0.0785 -0.2625 -1.9763 -0.6274 0.3952 -2.6035 -1.2818 271 H66 H67 C68 C69 C70 C71 C72 C73 H74 H75 H76 H77 H78 H79 H80 H81 0.4955 0.7802 6.2375 6.141 4.932 3.8019 3.9091 5.117 7.1833 7.0117 4.8661 3.0364 5.1812 3.2381 1.8185 1.6783 4.8022 5.1818 -4.0536 -2.7832 -2.0854 -2.6434 -3.9231 -4.6223 -4.6006 -2.3307 -1.0896 -4.387 -5.6197 -2.1591 -3.2185 -1.5675 -0.6851 -2.3907 -2.9477 -2.3709 -2.41 -3.0353 -3.6081 -3.5622 -2.9162 -1.8893 -1.9646 -4.0712 -4.0048 -5.6996 -5.7174 -6.3537 L*NiBr—propargyl, (R), trans Calculated geometry Ni1 O2 N3 N4 C5 Atom X 0 -0.7196 -0.9477 1.5967 -2.3189 Y 0 0.7406 0.2279 0.0978 0.5547 Z 0 -3.8823 -1.7121 -1.2262 -2.1301 272 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 Br17 H18 C19 C20 Si21 C22 C23 H24 H25 H26 C27 C28 C29 C30 C31 C32 H33 H34 H35 H36 H37 C38 C39 C40 C41 H42 H43 H44 H45 H46 H47 H48 -2.9844 -2.1641 -2.5318 -2.6109 -0.1721 1.2655 2.1953 1.8512 3.5544 3.9038 2.8833 -1.9089 3.1499 0.9218 1.923 1.6563 -0.0705 2.7736 0.4657 -0.5731 -0.8484 5.9094 4.6247 3.5897 3.8208 5.1249 6.1523 6.7168 4.4271 2.5873 5.3203 7.1505 4.5458 0.6525 1.652 3.4451 1.0766 0.6648 -0.3955 2.0622 0.6243 2.2578 3.8597 -0.2785 0.6696 -0.2188 1.5717 0.4191 0.2871 0.2993 0.4465 0.0914 -0.1313 -0.1199 -1.0503 -0.2667 0.3213 1.2987 -1.338 0.9657 2.1491 1.3252 1.8396 0.266 4.8018 5.3006 4.4387 3.0496 2.5608 3.4286 5.4803 6.372 4.8303 1.492 3.0275 0.076 -1.9543 -2.7185 -1.0674 -2.9045 -1.2323 -2.1326 -3.6394 -2.9263 -2.4818 -1.9977 -1.8641 -3.6685 -4.2018 -4.1043 -2.7167 -2.5272 -3.5554 -4.5803 -3.2783 -1.9284 -0.9606 0.9529 0.0801 1.7535 1.4554 2.388 2.7577 1.2205 3.6547 2.3095 3.0794 0.1319 0.3802 0.7434 0.8698 0.6233 0.255 -0.1556 0.2871 0.9317 0.722 0.0621 -4.4067 3.8648 1.091 2.9536 4.2317 4.6972 3.5782 1.54 0.756 0.2038 3.3782 273 H49 H50 C51 C52 C53 C54 C55 C56 H57 H58 H59 H60 H61 H62 H63 H64 H65 H66 H67 H68 H69 H70 C71 C72 C73 C74 C75 C76 H77 H78 H79 H80 H81 4.1003 3.4946 -2.8185 -1.9392 -2.4677 -3.9332 -4.8129 -4.2882 -2.7662 -1.9164 -0.8997 -1.8404 -2.3791 -4.3037 -4.0048 -4.8283 -5.8562 -4.3879 -4.9035 5.3556 4.0466 5.0138 7.8744 7.6391 6.3572 5.2872 5.5345 6.8177 8.8785 8.4566 6.1813 4.7169 6.9917 -0.7544 -0.2845 1.8189 3.0551 4.2714 4.5617 3.3291 2.1085 1.5756 3.2962 2.8449 5.1536 4.0753 5.4164 4.8597 3.0972 3.538 2.2939 1.2205 -0.6449 -0.172 1.0669 -0.8037 0.2304 0.4394 -0.3823 -1.4189 -1.6291 -0.9652 0.8871 1.2743 -2.0727 -2.442 2.125 3.7287 -1.4072 -1.647 -0.8771 -1.2193 -0.9821 -1.747 -0.3316 -2.7259 -1.3454 -1.0889 0.2074 -0.6283 -2.2823 0.0987 -1.2735 -2.8328 -1.5216 -4.2256 -5.3542 -4.5304 -0.4273 -1.3392 -1.8507 -1.4563 -0.5379 -0.0294 -0.0269 -1.6473 -2.53 -0.2267 0.6801 274 L*NiBr—propargyl, (S), cis Calculated geometry Ni1 O2 N3 N4 C5 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 Br17 H18 C19 C20 Si21 C22 Atom X 0 -1.9084 -1.207 0.4591 -1.9213 -2.6547 -2.63 -3.6793 -2.5675 -1.1959 -0.3616 -0.3748 -1.0483 0.4862 1.3325 1.274 2.0912 1.9202 -0.9986 -1.6303 -2.334 -0.2355 Y 0 1.4205 1.0485 -0.8319 2.3419 2.3099 2.3959 2.0703 3.3651 0.704 -0.4013 -0.9485 -0.5378 -2.0123 -2.4791 -1.8465 -0.6433 -2.1721 0.1308 1.3889 -1.2021 -0.2745 Z 0 -3.2141 -1.1131 -1.8231 -1.0354 -0.2235 -2.4054 -2.3539 -2.9142 -2.3565 -2.803 -4.0776 -4.8317 -4.387 -3.3553 -2.0997 0.89 -1.2828 1.7285 1.9666 1.3369 3.0137 275 C23 H24 H25 H26 C27 C28 C29 C30 C31 C32 H33 H34 H35 H36 H37 C38 C39 C40 C41 H42 H43 H44 H45 H46 H47 H48 H49 H50 C51 C52 C53 C54 C55 C56 H57 H58 H59 H60 H61 H62 H63 H64 H65 -2.1882 0.1726 0.6064 -0.9115 -4.0729 -4.7792 -4.169 -2.8289 -2.1317 -2.7494 -4.5526 -5.8147 -4.7197 -1.0956 -2.1919 0.4914 -3.2259 -3.6549 -1.5335 -4.0571 -2.5497 -3.6458 -4.5231 -4.0044 -3.2988 -2.2731 -1.1582 -0.6877 0.2194 -0.9299 -1.658 -0.689 0.4745 1.1919 -0.1875 0.7653 -0.4867 -2.4706 -2.1293 -1.2287 -0.2935 0.0831 1.1872 2.4382 -1.2923 0.4037 -0.2327 6.1933 5.1396 3.8995 3.688 4.7566 5.9933 7.1648 5.2864 3.0795 4.6061 6.8108 -2.5814 -1.6121 -0.6157 -2.7875 -2.3122 -2.0793 -0.6999 -1.2936 0.3989 -0.6125 -3.606 -2.6594 -3.0982 3.5885 3.4872 4.8356 5.9571 6.0583 4.7126 3.7875 2.6329 3.2548 4.7604 5.0902 6.9172 5.7543 6.376 6.8374 2.2645 2.9471 3.215 3.8854 2.8908 2.2984 2.1106 2.5084 3.1154 3.3011 3.0348 1.9795 1.6439 3.4266 3.7662 -5.7779 2.9582 0.1178 0.683 2.7678 3.6917 3.4142 0.1764 0.3676 -0.922 0.675 -0.3442 1.3171 -1.7687 -0.7536 -0.6285 -0.2408 -1.2332 -1.3892 -2.7775 -1.827 0.2295 0.1085 -1.5959 -0.1779 0.771 -2.2179 -0.9131 276 H66 H67 H68 H69 H70 C71 C72 C73 C74 C75 C76 H77 H78 H79 H80 H81 1.6838 1.9931 1.5012 -0.152 0.1032 4.1858 4.5731 3.6421 2.3103 1.9308 2.8614 4.9138 5.606 3.9531 0.8955 2.5484 4.4504 4.7889 -2.8885 -3.4748 -1.846 -5.666 -4.4368 -3.4045 -3.5819 -4.8231 -5.8567 -6.4748 -4.2788 -2.4436 -4.991 -6.8185 -0.4344 -2.1436 -6.0852 -5.839 -6.4969 -3.7873 -3.2443 -3.1113 -3.5288 -4.0696 -4.1952 -3.89 -2.9235 -2.6938 -4.3721 -4.6096 L*NiBr—propargyl, (S), trans Calculated geometry Ni1 O2 N3 N4 Atom X 0 -1.8469 -1.3545 0.9524 Y 0 -0.1441 0.2081 -0.9894 Z 0 -3.5769 -1.419 -1.5037 277 C5 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 Br17 H18 C19 C20 Si21 C22 C23 H24 H25 H26 C27 C28 C29 C30 C31 C32 H33 H34 H35 H36 H37 C38 C39 C40 C41 H42 H43 H44 H45 H46 H47 -2.5666 -3.3158 -3.0099 -3.8461 -3.2453 -1.0328 0.22 0.6256 -0.0171 1.8499 2.6145 2.1182 -1.6892 2.6997 1.5504 2.235 2.5555 1.2376 2.7906 0.6292 0.6922 2.1762 4.6135 4.9548 4.3645 3.4092 3.0745 3.6723 5.0783 5.6888 4.6381 2.3381 3.4 2.3024 4.2737 2.8326 1.6399 4.861 4.2132 4.8253 3.4035 3.4207 1.892 1.0149 0.7373 0.5626 -0.1508 1.3845 -0.3186 -1.0513 -1.734 -1.7244 -2.4176 -2.3595 -1.6349 0.3686 -1.5935 0.2537 -0.9849 1.6312 0.8212 -2.0383 1.7322 0.0871 1.0581 -5.7784 -5.0849 -3.855 -3.29 -4 -5.2281 -6.7419 -5.5024 -3.3191 -3.5752 -5.7621 -3.1471 1.7223 1.4901 3.2672 2.547 1.8866 0.7824 2.3837 0.6074 1.4814 -1.6286 -0.8745 -3.0432 -3.0207 -3.7306 -2.543 -2.6439 -3.7804 -4.662 -3.7891 -2.6074 -1.511 1.6044 -0.5933 1.2527 1.4636 0.3485 2.6667 1.7564 2.626 3.2762 3.2004 2.6329 1.4659 1.1762 2.0516 3.2279 3.5115 2.8579 0.7718 0.2681 3.9141 4.4261 -5.0209 1.1398 -1.5195 0.6111 0.7017 2.2277 0.9696 -1.8245 -1.8082 -2.0896 278 H48 H49 H50 C51 C52 C53 C54 C55 C56 H57 H58 H59 H60 H61 H62 H63 H64 H65 H66 H67 H68 H69 H70 C71 C72 C73 C74 C75 C76 H77 H78 H79 H80 H81 2.0941 0.5815 1.6731 -1.1944 -2.2587 -3.5451 -3.2639 -2.2075 -0.9212 -1.532 -0.2597 -1.8552 -4.2699 -4.0174 -4.1983 -2.9042 -2.6092 -1.9921 -0.4647 -0.1816 3.3882 2.0816 1.7818 6.4452 6.3066 5.0617 3.9418 4.0916 5.3343 7.4171 7.1693 4.9562 3.2243 5.4338 4.056 3.174 3.6013 3.0345 2.5153 3.3512 4.8438 5.3568 4.529 2.8755 2.4637 2.6221 2.9896 3.2079 5.4216 5.0033 5.2947 6.4222 4.6748 4.8826 -3.0516 -4.2244 -2.7688 -4.2292 -2.8472 -2.2415 -3.0093 -4.396 -5.0015 -4.705 -2.2371 -1.1622 -5.0078 -6.0835 -0.0115 0.3184 1.6597 -2.4472 -1.4691 -1.5505 -1.344 -2.3285 -2.2386 -3.488 -2.3253 -0.4471 -0.8011 -2.5404 -1.4441 -0.3107 -3.3574 -2.1393 -1.2432 -2.9767 -5.1666 -4.9383 -5.912 -2.0733 -1.9113 -2.0981 -2.4603 -2.6263 -2.4292 -1.9194 -1.6322 -1.965 -2.8846 -2.5466 279 L*NiBr—allenyl, (R), cis Calculated geometry Ni1 O2 N3 N4 C5 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 Br17 H18 C19 C20 Si21 C22 C23 C24 C25 Atom X 0 1.3471 1.1321 -1.1686 2.4615 2.5005 2.4716 2.2803 3.3778 0.6482 -0.632 -1.2471 -0.7722 -2.4785 -3.0324 -2.3348 -1.4961 -2.7336 0.8862 1.1076 -0.4006 1.5682 1.2068 4.1046 4.1227 Y 0 3.6874 1.5425 1.2093 1.9171 1.6836 3.4491 4.0216 3.8273 2.5624 2.4398 3.4443 4.4241 3.1956 1.9047 0.9608 -1.8105 -0.0452 -0.4832 -0.7231 -1.5815 0.6347 -0.9942 -3.6499 -3.396 Z 0 -0.6143 -0.0008 -1.1493 0.5172 1.5897 0.2875 1.2064 -0.2006 -0.6232 -1.3094 -2.04 -2.1112 -2.6673 -2.5151 -1.7373 -0.0275 -1.5908 3.6609 2.3805 4.5161 4.4305 1.1037 -0.6592 0.7194 280 C26 C27 C28 C29 H30 H31 H32 H33 H34 C35 C36 C37 C38 H39 H40 H41 H42 H43 H44 H45 H46 H47 H48 H49 H50 C51 C52 C53 C54 C55 C56 H57 H58 H59 H60 H61 H62 H63 H64 H65 H66 H67 C68 3.1744 2.1792 2.1731 3.1216 4.8501 4.8853 3.2008 1.4153 3.0942 -0.4257 -2.1009 0.0452 -3.1533 2.1372 2.264 0.8277 -1.1676 -0.6898 0.5615 -2.8765 -2.0977 -2.3853 -0.6866 1.0432 0.0515 3.6189 3.5849 4.951 6.0564 6.0964 4.7317 3.7866 2.6449 3.3733 4.9048 5.1971 7.0335 5.8695 6.3869 6.8719 4.4919 4.7647 -6.7648 -2.5503 -1.9282 -2.1987 -3.0476 -4.3106 -3.8612 -2.3497 -1.7248 -3.2358 -3.284 -0.7706 -1.7312 4.2973 0.2404 1.2061 1.3421 -3.9376 -3.1991 -3.7698 -1.3517 0.2508 -0.7071 -2.3672 -2.1826 -0.7449 1.3274 1.1374 1.4399 0.5919 0.78 0.4855 2.3925 1.0493 0.0767 1.2527 2.511 0.8441 -0.4733 1.8228 0.1338 -0.5838 0.6655 0.6262 1.2931 0.5081 -0.8742 -1.4503 -1.1094 1.3507 2.3675 -1.5015 -2.5272 3.7084 4.3465 6.3478 -3.4347 5.2902 3.7958 4.8455 4.1976 2.6421 3.7799 4.8744 4.7627 3.283 6.8743 6.4782 6.8411 -1.707 -0.1842 0.4487 -0.1911 -1.7117 -2.3441 -1.9529 -2.1428 0.0062 1.5355 0.3226 0.2546 0.0383 -1.9405 -2.1571 -2.2074 -3.432 -4.2232 281 C69 C70 C71 C72 C73 H74 H75 H76 H77 H78 H79 H80 H81 -6.5029 -5.2914 -4.3258 -4.598 -5.8072 -7.7121 -7.2458 -5.0962 -3.8496 -5.9997 -4.2475 -2.8121 -2.91 0.4264 0.8498 1.4889 1.6817 1.2515 0.2928 -0.0608 0.6974 2.1479 1.4007 4.2411 5.2799 4.2327 -2.864 -2.3136 -3.1126 -4.4786 -5.0287 -4.6548 -2.2272 -1.2491 -5.122 -6.0943 -3.3465 -3.0787 -4.5084 L*NiBr—allenyl, (R), trans Calculated geometry Ni1 O2 N3 N4 C5 H6 C7 Atom X 0 1.2832 1.1249 -1.1863 2.5166 2.7142 2.5289 Y 0 3.753 1.6066 1.2044 1.9485 1.7088 3.483 Z 0 -0.5477 0.0766 -0.996 0.3986 1.4534 0.1706 282 H8 H9 C10 C11 C12 H13 C14 C15 C16 Br17 H18 C19 C20 Si21 C22 C23 C24 C25 C26 C27 C28 C29 H30 H31 H32 H33 H34 C35 C36 C37 C38 H39 H40 H41 H42 H43 H44 H45 H46 H47 H48 H49 H50 2.497 3.3569 0.5808 -0.7567 -1.527 -1.1289 -2.8196 -3.2631 -2.3947 1.264 -2.7025 0.0322 -0.6032 1.2576 -0.127 -1.1049 -4.9599 -4.561 -3.3019 -2.4018 -2.8143 -4.0771 -5.9496 -5.242 -3.0025 -2.1313 -4.3731 0.8059 2.9923 1.2111 -3.6655 -0.5184 -0.8097 0.8469 1.5087 0.8436 -0.2122 3.7524 3.2597 3.0386 1.9211 0.2044 1.4841 4.0546 3.8433 2.6303 2.4897 3.519 4.535 3.2579 1.9172 0.9405 -1.2037 -0.1018 -2.826 -2.19 -4.1823 -2.4517 -1.5182 -2.0555 -2.8827 -2.7298 -1.7442 -0.9295 -1.0814 -2.1725 -3.6492 -3.3685 -0.1624 -0.4323 -4.8736 -3.429 -5.5523 4.3945 -3.2977 -1.597 -2.1829 -5.6706 -4.0775 -5.297 -4.1886 -2.989 -2.6316 -6.3569 -5.9974 -5.1667 1.1089 -0.4525 -0.4774 -1.0435 -1.5608 -1.5578 -2.0457 -2.0044 -1.4863 1.5725 -1.4746 -2.337 -1.3678 -1.8414 -3.8012 -0.3633 1.4688 0.4095 -0.1685 0.2925 1.3656 1.9453 1.9182 0.0288 -1.0038 1.7381 2.7741 -0.1489 -1.7922 -3.1443 -2.545 -4.3926 -3.933 -4.2485 0.1471 0.6113 -0.1546 -1.5416 -2.7673 -1.0326 -2.8877 -3.2162 -4.1407 283 C51 C52 C53 C54 C55 C56 H57 H58 H59 H60 H61 H62 H63 H64 H65 H66 H67 H68 H69 H70 C71 C72 C73 C74 C75 C76 H77 H78 H79 H80 H81 3.2709 3.4844 4.9466 5.9071 5.6949 4.2353 3.4284 2.2302 3.2573 5.0812 5.1943 6.951 5.7373 5.9701 6.3662 3.9921 4.0881 -4.7259 -3.3208 -3.6009 -7.1463 -6.5816 -5.3238 -4.6112 -5.1865 -6.4433 -8.1309 -7.1215 -4.8962 -4.6388 -6.873 1.317 1.1255 1.3839 0.5113 0.7005 0.4451 2.3777 1.0708 0.0719 1.1968 2.4486 0.7392 -0.5498 1.7354 0.034 -0.6176 0.625 4.2495 5.3481 4.4784 0.4963 0.1027 0.577 1.4597 1.8457 1.3655 0.1244 -0.5766 0.2689 2.5029 1.6681 -1.9806 -0.4717 -0.0802 -0.8967 -2.4029 -2.7939 -2.251 -2.2491 -0.2342 0.999 -0.2494 -0.6224 -0.6372 -2.681 -2.9706 -2.6159 -3.8722 -2.2933 -2.1207 -3.6427 -3.18 -1.9622 -1.5871 -2.4223 -3.6456 -4.0208 -3.475 -1.2977 -0.63 -4.3228 -4.9793 284 L*NiBr—allenyl, (S), cis Calculated geometry Ni1 O2 N3 N4 C5 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 Br17 H18 C19 C20 C21 Si22 C23 Atom X 0 1.4719 1.2315 -1.2631 2.6815 3.0225 2.7461 2.7852 3.5506 0.6989 -0.7021 -1.3961 -0.8923 -2.7406 -3.3229 -2.5362 -1.5306 -2.9518 0.6511 0.9902 -0.3021 1.3366 1.225 Y 0 3.6015 1.445 1.3055 1.6831 1.3209 3.2247 3.6982 3.618 2.5307 2.5252 3.6153 4.5796 3.4718 2.1936 1.1567 -1.7822 0.1567 -0.5947 -0.7669 -1.5528 0.8659 -0.9552 Z 0 -0.7919 -0.2359 -0.922 -0.1064 0.8706 -0.1803 0.8115 -0.8125 -0.6837 -1.0853 -1.5863 -1.6709 -1.9654 -1.8119 -1.2742 0.0439 -1.1339 3.6578 2.3904 4.359 4.6381 1.1179 285 C24 C25 C26 C27 C28 C29 H30 H31 H32 H33 H34 H35 H36 H37 C38 C39 C40 C41 H42 H43 H44 H45 H46 H47 H48 H49 H50 C51 C52 C53 C54 C55 C56 H57 H58 H59 H60 H61 H62 H63 H64 H65 H66 4.4876 4.6316 3.5692 2.3337 2.2044 3.2657 5.3222 5.5833 3.691 1.2555 3.1403 -0.6312 -1.2003 0.171 -3.4945 2.4349 2.3315 -0.1104 2.8205 1.8741 3.2977 2.7167 3.1909 1.7019 0.2518 -0.7824 -0.7049 3.4686 3.1004 3.8939 5.4041 5.7768 4.9813 3.2043 3.3136 2.0196 3.6365 3.5945 5.9537 5.7189 5.5652 6.8589 5.2879 -3.2067 -2.5669 -1.848 -1.7475 -2.3978 -3.1216 -3.7635 -2.6219 -1.3378 -2.3249 -3.6175 -2.3626 -1.0229 -2.0103 4.6649 0.2211 2.001 1.827 1.0521 -0.4584 -0.3351 2.8666 1.47 2.3791 2.6915 2.2036 1.1905 0.9438 1.3602 0.5441 0.66 0.2577 1.0596 -0.1171 2.4342 1.2221 0.8709 -0.5173 0.0387 1.7055 -0.8167 0.3916 2.1215 -0.5536 0.6838 1.2336 0.5607 -0.6832 -1.2304 -0.9874 1.2201 2.1926 -1.2182 -2.197 3.6896 4.7219 5.2459 -2.4818 6.0362 3.5104 5.3869 6.6514 6.6996 5.6328 4.0747 3.0708 2.6895 5.969 4.5973 6.0632 -1.2032 -2.6347 -3.663 -3.4285 -1.9973 -0.9612 -1.0968 -2.7866 -2.8047 -4.6847 -3.5861 -4.1561 -3.6071 -1.8539 -1.8288 -1.0098 286 H67 H68 H69 H70 C71 C72 C73 C74 C75 C76 H77 H78 H79 H80 H81 5.2186 -4.5489 -3.0326 -3.4803 -7.3812 -6.8642 -5.5474 -4.7291 -5.2581 -6.5728 -8.4112 -7.489 -5.1522 -4.6302 -6.9659 0.708 4.6424 5.5964 4.6908 1.21 0.8679 1.1963 1.8812 2.2172 1.882 0.951 0.3434 0.9324 2.7216 2.1425 0.0571 -2.172 -2.1244 -3.5842 -2.8342 -1.5805 -1.2516 -2.1684 -3.4271 -3.757 -3.0929 -0.8531 -0.2674 -4.1638 -4.7431 L*NiBr—allenyl, (S), trans Calculated geometry Ni1 O2 N3 N4 C5 Atom X 0 1.2467 1.1302 -1.2569 2.5383 Y 0 3.7557 1.6079 1.2144 1.9539 Z 0 -0.6195 0.0117 -0.8851 0.2498 287 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 Br17 H18 C19 C20 C21 Si22 C23 C24 C25 C26 C27 C28 C29 H30 H31 H32 H33 H34 H35 H36 H37 C38 C39 C40 C41 H42 H43 H44 H45 H46 H47 H48 2.7995 2.5324 2.553 3.3215 0.5518 -0.8191 -1.6088 -1.2021 -2.9277 -3.3795 -2.4953 1.3759 -2.8155 -0.0557 -0.6397 0.9287 -0.4021 -1.1139 -4.8999 -4.5724 -3.3355 -2.3877 -2.7296 -3.9694 -5.8719 -5.2918 -3.0922 -2.0095 -4.2102 1.067 1.9165 0.591 -1.0491 -1.6606 1.2193 -1.2234 -0.328 -2.0012 -1.9202 -2.5885 -1.25 1.07 1.6166 1.7128 3.4888 4.0585 3.8529 2.6317 2.4939 3.5199 4.5317 3.2608 1.9268 0.9553 -1.226 -0.0804 -2.8178 -2.1968 -3.9571 -2.2291 -1.5212 -2.0701 -2.8388 -2.6832 -1.7533 -0.9952 -1.1505 -2.189 -3.5609 -3.2749 -0.2697 -0.5466 -4.1784 -3.7106 -4.8803 -3.6789 -0.8255 -1.6093 -3.3723 -4.5131 -4.0574 -0.5414 -1.1138 0.0635 -1.267 -0.7644 1.2904 0.0245 0.9644 -0.6449 -0.5069 -0.9855 -1.4793 -1.5214 -1.8898 -1.7918 -1.2933 1.4593 -1.2384 -2.3482 -1.3373 -2.1319 -4.11 -0.3227 1.6454 0.5199 -0.1041 0.3762 1.5136 2.1397 2.1313 0.1234 -0.9907 1.8993 3.019 -1.0622 -2.5599 -2.6345 -5.137 -4.1029 -4.8613 -6.1826 -5.1456 -4.7287 -5.1365 -3.5837 -3.5996 -5.8996 -4.2754 288 H49 H50 C51 C52 C53 C54 C55 C56 H57 H58 H59 H60 H61 H62 H63 H64 H65 H66 H67 H68 H69 H70 C71 C72 C73 C74 C75 C76 H77 H78 H79 H80 H81 1.9856 -3.7878 3.151 3.4595 4.9395 5.8628 5.5546 4.0784 3.2739 2.1003 3.2613 5.1429 5.1605 6.9174 5.7283 5.7924 6.2014 3.8643 3.8607 -4.8376 -3.421 -3.7677 -7.2956 -6.6907 -5.4238 -4.7426 -5.3578 -6.6237 -8.2871 -7.2056 -4.9635 -4.8338 -7.0846 -2.4021 4.3921 1.3228 1.1391 1.4192 0.5627 0.7469 0.465 2.385 1.058 0.0835 1.2345 2.4875 0.8093 -0.5011 1.7864 0.0926 -0.602 0.6371 4.2581 5.3517 4.4541 0.4725 0.1091 0.5967 1.4632 1.8184 1.3249 0.0896 -0.5578 0.3098 2.4607 1.6031 -4.8734 -2.376 -2.1707 -0.6773 -0.3762 -1.2504 -2.7404 -3.0399 -2.4528 -2.3746 -0.4235 0.6926 -0.5591 -1.0411 -0.9813 -3.0348 -3.3492 -2.8461 -4.1072 -2.0781 -1.9849 -3.477 -2.8027 -1.595 -1.2711 -2.148 -3.3613 -3.6852 -3.0577 -0.8988 -0.3227 -4.0709 -4.6365 289 L*NiI—Br Calculated geometry Ni1 O2 N3 N4 C5 H6 C7 H8 H9 C10 C11 C12 H13 C14 C15 C16 C17 H18 Br19 H20 H21 H22 Atom X 0 -3.0017 -1.7935 0.4796 -3.1745 -3.2413 -3.9735 -4.341 -4.8056 -1.8241 -0.5891 -0.4962 -1.3967 0.7477 0.8332 1.8678 1.6658 -2.8518 1.245 2.512 1.5842 1.1243 Y 0 2.1138 0.7798 1.269 0.5576 0.8031 1.591 2.4368 1.1607 1.6069 1.949 2.858 3.3618 3.111 4.0747 2.413 1.5018 -1.4935 -1.5457 0.9467 3.7583 5.0797 Z 0 1.6307 0.2876 1.5016 -0.164 -1.2357 0.6775 0.0797 1.2495 1.2719 1.9775 3.022 3.3772 3.6211 4.7719 3.1133 2.06 -0.593 -1.1915 1.647 5.5098 4.4238 290 H23 C24 C25 C26 C27 C28 C29 H30 H31 H32 H33 H34 C35 C36 C37 C38 C39 C40 H41 H42 H43 H44 H45 H46 H47 H48 H49 H50 -0.1428 5.8819 5.1415 3.8327 3.2443 4.0007 5.3075 6.9053 5.5871 3.272 3.5541 5.8782 -5.3658 -4.9768 -3.5789 -3.4754 -3.8651 -5.2616 -4.6926 -6.3869 -5.7219 -5.011 -2.4501 -4.1436 -3.1254 -3.8156 -6.0127 -5.5062 4.1686 2.8388 3.974 3.8438 2.5738 1.4385 1.5706 2.9426 4.968 4.7353 0.4453 0.6783 -2.6608 -1.1826 -0.9169 -1.4157 -2.8946 -3.155 -3.2623 -2.8147 -0.5703 -0.8588 -1.2661 -0.8194 -3.504 -3.2186 -2.6283 -4.2293 5.2692 4.5945 4.248 3.7792 3.6451 3.9878 4.4628 4.9642 4.3379 3.4921 3.8955 4.7327 -0.4531 -0.5708 0.0089 1.458 1.5696 0.9941 -1.0911 -0.8411 -0.0291 -1.6253 1.8344 2.1064 1.0184 2.6228 1.6123 1.0505 trimethyl(4-phenylbut-1-en-3-yn-2-yl)silane TMS Ph Calculated geometry C1 C2 Si3 C4 Atom X 0 -1.0938 1.3574 0.0655 Y 0 0.1429 -1.2288 0.6978 Z 0 0.9048 0.5433 -1.1559 291 C5 C6 C7 C8 C9 C10 C11 H12 H13 H14 H15 H16 C17 C18 C19 H20 H21 H22 H23 H24 H25 H26 H27 H28 H29 H30 -1.9842 -5.0881 -5.3957 -4.3798 -3.031 -2.7315 -3.7541 -5.8865 -6.4355 -4.6192 -1.6902 -3.5079 2.018 2.7275 0.5595 -0.7178 0.9084 2.7738 2.4884 1.2045 3.5158 2.3484 3.1928 1.2937 -0.276 0.1688 0.2011 0.4524 0.1928 0.112 0.2896 0.5491 0.6302 0.5152 0.0519 -0.0907 0.6856 0.8327 -0.6587 -1.2542 -2.9287 1.4045 0.5802 -1.3652 0.3353 -0.5953 -1.963 -1.5724 -0.2614 -3.6697 -2.9021 -3.2779 1.7401 4.6263 3.2857 2.3328 2.7103 4.0654 5.011 5.37 2.9797 1.2866 4.3653 6.0566 2.2139 -0.7476 0.7078 -1.4523 -1.8429 2.5963 2.1353 2.9552 -0.4431 -1.7325 -0.861 1.0665 1.4261 -0.2622 trimethyl(4-phenylbut-1-en-3-yn-2-yl)silyl radical TMS Me Ph Calculated geometry C1 C2 Si3 C4 C5 C6 Atom X 0 -1.0081 1.7906 -0.2974 -1.8955 -4.8818 Y 0 0.3926 0.0943 -0.5131 0.7642 2.0264 Z 0 0.835 0.608 -1.3892 1.6231 4.3478 292 C7 C8 C9 C10 C11 H12 H13 H14 H15 H16 C17 C18 C19 H20 H21 H22 H23 H24 H25 H26 H27 H28 H29 H30 H31 -5.2439 -4.2681 -2.893 -2.5422 -3.528 -5.6518 -6.2986 -4.5505 -1.4872 -3.2412 1.8628 2.8386 2.4 -1.3644 -0.0106 0.2912 2.8986 1.5003 1.2394 3.8947 2.7952 2.4896 3.458 1.8092 2.3187 1.5426 1.1261 1.185 1.6781 2.0912 2.3519 1.4906 0.7489 1.7288 2.4682 1.11 0.8858 -1.6661 -0.745 0.2375 -1.4192 1.1695 2.1369 0.6571 0.9467 0.2952 1.9069 -1.6601 -2.1499 -2.2834 3.083 2.1812 2.529 3.8136 4.7058 5.0519 2.7998 1.1958 4.092 5.6911 2.1919 -0.7488 0.9257 -1.5302 -2.1496 -1.616 2.566 2.0208 2.9802 -0.4356 -1.6788 -0.9754 1.239 1.721 0.0157 3.1.6.3 Geometries of calculated species for BDE estimation These geometries were calculated using calculation method B. 4-iodotetrahydro-2H-pyran O I Calculated geometry O1 C2 C3 Atom X 0 -1.3522 -2.2913 Y 0 0.006 0.5058 Z 0 -0.4251 0.6774 293 C4 C5 C6 H7 H8 H9 H10 I11 H12 H13 H14 H15 H16 -2.0974 -0.6352 0.2021 -1.6475 -1.4004 -3.3251 -2.0534 -3.3464 -2.484 -0.3032 -0.481 -0.0428 1.2655 -0.3513 -0.4001 -0.8443 -1.0054 0.6617 0.4671 1.5476 0.3682 -1.3565 0.5902 -1.0887 -1.8834 -0.7969 1.9163 2.3242 1.1205 -0.7429 -1.2947 0.3292 0.9031 3.5679 1.7523 2.6436 3.157 0.8531 1.3559 4-iodotetrahydro-2H-pyran radical O Calculated geometry O1 C2 C3 C4 C5 C6 H7 H8 H9 H10 H11 H12 H13 H14 H15 Atom X Y 0 -1.3252 -2.356 -2.0893 -0.6726 0.2325 -1.5153 -1.3784 -3.3668 -2.2788 -2.8997 -0.3213 -0.5564 0.059 1.2855 0 -0.0784 0.267 -0.5107 -0.6541 -0.9302 -1.0908 0.6224 0.0907 1.3482 -0.8004 0.2768 -1.4474 -1.9516 -0.8342 1-(3-bromo-4,4,4-trifluorobutyl)-4-methoxybenzene CF3 Br O Z 0 -0.5021 0.5799 1.8205 2.2537 1.0465 -0.8866 -1.3358 0.2028 0.7816 2.4762 2.7286 2.9968 0.6782 1.3128 294 Calculated geometry C1 C2 C3 C4 C5 C6 H7 O8 H9 H10 C11 H12 C13 H14 H15 H16 C17 H18 H19 C20 H21 H22 C23 Br24 H25 F26 F27 F28 Atom X Y 0 0.3821 -0.5343 -1.81 -2.2162 -1.2908 0.6892 1.6127 -0.2216 -2.5063 -3.625 -1.5742 2.5807 3.4716 2.8181 2.2451 -4.5926 -3.6523 -3.9659 -6.0416 -4.5457 -4.2827 -7.0126 -6.3144 -6.3477 -6.7606 -8.2904 -6.9087 0 -1.1747 -2.2221 -2.087 -0.9146 0.1154 0.8239 -1.3975 -3.1323 -2.9126 -0.7604 1.0348 -0.3664 -0.749 -0.1259 0.5406 -0.3518 -0.0142 -1.7033 -0.2593 -1.0966 0.5996 -0.1003 1.2283 -1.1493 0.9893 -0.0387 -1.1755 Z 0 0.6427 0.7596 0.2451 -0.3989 -0.5109 -0.1125 1.1797 1.2543 0.3416 -0.9091 -1.0104 1.0942 1.587 0.0533 1.6064 0.2083 -1.7045 -1.3482 -0.2433 1.0077 0.6436 0.9204 -1.5061 -0.7901 1.6617 0.5168 1.7363 1-(3-bromo-4,4,4-trifluorobutyl)-4-methoxybenzene radical CF3 O Calculated geometry C1 Atom X 0 Y 0 Z 0 295 C2 C3 C4 C5 C6 H7 O8 H9 H10 C11 H12 C13 H14 H15 H16 C17 H18 H19 C20 H21 H22 C23 Br24 H25 F26 F27 0.6137 -0.1279 -1.4602 -2.0956 -1.3426 0.5496 1.9171 0.3635 -2.0189 -3.5568 -1.8065 2.7177 3.707 2.7876 2.329 -4.4546 -3.7637 -3.8393 -5.9001 -4.2387 -4.1656 -6.6325 -6.431 -6.1518 -7.9441 -6.5342 -1.2441 -2.4025 -2.3106 -1.0727 0.07 0.9133 -1.4313 -3.362 -3.2205 -0.9821 1.045 -0.2887 -0.6637 0.3497 0.2986 -1.0388 -0.0521 -1.801 -0.9645 -1.9749 -0.2251 0.3172 -1.799 1.2299 0.1646 0.9121 0.1263 -0.1147 -0.4729 -0.6047 -0.3618 0.1739 0.4713 -0.0205 -0.6618 -0.9487 -0.4599 0.7183 0.9704 -0.1678 1.556 0.3229 -1.4802 -1.6148 0.0108 0.8462 0.991 0.0724 -0.4266 -0.8213 -0.1938 1.2872 1-(3-bromo-4,4-difluorobutyl)-4-methoxybenzene F F Br O Calculated geometry C1 C2 Atom X 0 0.4165 Y 0 -1.1847 Z 0 0.6021 296 C3 C4 C5 C6 H7 O8 H9 H10 C11 H12 C13 H14 H15 H16 C17 H18 H19 C20 H21 H22 C23 Br24 H25 F26 H27 F28 -0.4697 -1.7506 -2.1907 -1.2942 0.6655 1.6552 -0.1307 -2.4247 -3.6049 -1.6048 2.5896 3.4932 2.8177 2.2261 -4.5581 -3.6398 -3.9526 -6.0068 -4.5251 -4.2268 -6.9789 -6.2778 -6.3317 -6.5902 -8.0028 -6.9787 -2.2604 -2.1436 -0.9628 0.0959 0.8464 -1.3901 -3.1774 -2.9901 -0.825 1.0233 -0.3265 -0.6984 -0.0395 0.5498 -0.3685 -0.1092 -1.7829 -0.2608 -1.0923 0.5858 -0.0308 1.2052 -1.1534 1.0152 0.1478 -1.1491 0.6854 0.1781 -0.426 -0.505 -0.0854 1.1291 1.1491 0.2495 -0.9248 -0.9727 1.0818 1.5595 0.0506 1.6274 0.1859 -1.748 -1.324 -0.2528 1.0062 0.597 0.8919 -1.5568 -0.7851 1.6714 0.5612 1.6887 1-(3-bromo-4,4-difluorobutyl)-4-methoxybenzene radical F F O Calculated geometry C1 C2 Atom X 0 0.6087 Y 0 -1.2418 Z 0 0.1646 297 C3 C4 C5 C6 H7 O8 H9 H10 C11 H12 C13 H14 H15 H16 C17 H18 H19 C20 H21 H22 C23 H24 F25 H26 F27 -0.1341 -1.4632 -2.0943 -1.3394 0.5506 1.9093 0.3533 -2.0234 -3.5532 -1.8007 2.7083 3.6938 2.7905 2.3099 -4.4606 -3.755 -3.8303 -5.9035 -4.2561 -4.1721 -6.6557 -6.4096 -6.0758 -7.7033 -6.6178 -2.404 -2.3177 -1.0822 0.0642 0.9162 -1.4232 -3.3621 -3.2307 -0.9951 1.0372 -0.2761 -0.6456 0.3402 0.3328 -1.0335 -0.0708 -1.8217 -0.9436 -1.9677 -0.2172 0.3123 -1.7689 1.3406 0.2543 0.7353 -0.052 -0.424 -0.5934 -0.3746 0.1547 0.5259 0.0724 -0.5927 -0.9486 -0.5006 0.7545 1.0286 -0.1462 1.5721 0.3137 -1.4922 -1.608 -0.0151 0.8472 0.9783 0.1603 -0.4999 -0.5674 -0.1374 1.4734 1-(3-bromobutyl)-4-methoxybenzene Me Br O Calculated geometry C1 C2 C3 C4 C5 C6 H7 Atom X 0 0.4315 -0.4425 -1.7254 -2.1803 -1.2956 0.6556 Y 0 -1.1945 -2.2815 -2.1669 -0.9775 0.0931 0.8559 Z 0 0.5713 0.6294 0.1253 -0.4502 -0.5019 -0.0655 298 O8 H9 H10 C11 H12 C13 H14 H15 H16 C17 H18 H19 C20 H21 H22 C23 Br24 H25 H26 H27 H28 1.6748 -0.092 -2.3886 -3.5933 -1.6173 2.6017 3.5137 2.8148 2.2401 -4.56 -3.6297 -3.9337 -6.0132 -4.525 -4.2276 -6.9587 -6.2183 -6.3248 -6.686 -7.9894 -6.9022 -1.3992 -3.2063 -3.0235 -0.844 1.0276 -0.3292 -0.7037 -0.0217 0.535 -0.4006 -0.1227 -1.8007 -0.2858 -1.1335 0.5494 -0.0045 1.1687 -1.1714 0.9181 0.0823 -0.8267 1.0897 1.0687 0.174 -0.9531 -0.9476 1.0503 1.5098 0.0217 1.6163 0.1503 -1.771 -1.3612 -0.273 0.9655 0.5771 0.8767 -1.6355 -0.825 1.391 0.5355 1.5967 1-(3-bromobutyl)-4-methoxybenzene radical Me O Calculated geometry C1 C2 C3 C4 C5 C6 H7 O8 H9 H10 C11 H12 C13 Atom X 0 0.4728 -0.3761 -1.6749 -2.1725 -1.3119 0.6349 1.7353 0.0062 -2.3186 -3.6026 -1.6655 2.6358 Y 0 -1.2018 -2.3089 -2.2072 -1.0105 0.0797 0.8721 -1.3956 -3.239 -3.0789 -0.8976 1.0211 -0.3034 Z 0 0.52 0.5677 0.1036 -0.4207 -0.4619 -0.056 0.9964 0.9678 0.1443 -0.8764 -0.8674 0.9693 299 H14 H15 H16 C17 H18 H19 C20 H21 H22 C23 H24 H25 H26 H27 3.5684 2.8141 2.2699 -4.5717 -3.688 -3.9162 -5.994 -4.4521 -4.2613 -7.0314 -6.3047 -6.7106 -7.9785 -7.2408 -0.6711 0.0438 0.5327 -0.5727 -0.121 -1.8346 -0.4811 -1.3398 0.3638 0.0744 -1.0105 1.0236 0.2431 -0.5993 1.3916 -0.0533 1.5737 0.2714 -1.641 -1.3465 -0.15 1.0558 0.7536 0.757 -1.0441 1.2011 0.242 1.6035 300 2: Copper-catalyzed C-N coupling 2.1: Background (A) O H N N N Me Me NH N MeO N Me Me N H2N Me O alkyl1 N H alkyl2 (C) alkyl1 N H alkyl2 X alkyl3 common X alkyl3 H (alkyl5) alkyl4 cat. CuBr, P/L CsOPh•H2O hν 440 (nm) ° Et2O, -10 C OH OMe MeO O Me N Me N Me Valbenazine (tardive dyskinesia) Osimertinib (anticancer) (B) N OMe alkyl1 N alkyl2 alkyl3 alkyl1 N H alkyl2 X Quinine (antimalarial) alkyl3 H (alkyl5) alkyl1 alkyl4 N difficult alkyl2 O alkyl1 N alkyl2 alkyl3 5 H(alkyl ) alkyl4 O PAr2 PAr2 O O P alkyl3 5 H(alkyl ) 4 alkyl OH O Me OMe L Ar = (3,5-di-t-butyl-4-methoxyphenyl) Figure 2.1.1: (A) Representative alkaloids of pharmaceutical interest. (B) Difficulty of nucleophilic substitution of secondary amines by secondary or tertiary electrophiles. (C) Developed photocatalytic method for general synthesis of alkyl C-N bonds. Tertiary amines are a widespread motif in pharmaceuticals42–44 as well as natural products, especially well represented in the rich chemistry of alkaloids (Fig 2.1.1A)45–47. The coupling of secondary amines with primary electrophiles is an elemental and widely used method for the synthesis of tertiary alkylamines48. However, attempted substitution of secondary or tertiary electrophiles often results in elimination products and poor yields. Reductive amination reactions and ameliorate some of these difficulties49, general solutions do not exist (Fig 2.1.1B). In recent 301 years, progress has been reported in the coupling of amine nucleophiles with unactivated electrophiles20,50–55. However, at the start of this project the only example published of the coupling of333333 alkylamines with unactivated secondary alkyl halides was limited to primary amines nuleophiles56. It should be noted that since publication of this work, further progress has been made in this area54,57,58. To address this gap in the literature, our group sought to accomplish the general coupling of secondary amines with secondary and tertiary unactivated alkyl bromides. Leveraging a dual-ligand methodology strategy previously used in our group,55 we discovered that copper under the influence of light and in the presence of a base, a phosphine photocatalyst P and secondary salicylate ligand L, the desired coupling could be achieved with a broad scope and under mild conditions (Fig 2.1.1C)54. In developing this reaction, certain mechanistic questions arose which were of interest. Specifically, we were interested to understand the difference in photoactivity between CuI species in solution, and we wanted to explore how the secondary ligand promotes the C—N coupling step. 2.2: Computational investigations of the photocatalyst O Ar Ar P CuI P ArAr O O O I O O PCu OPh ) = -2.4 V (vs Fc+ II/I E1/2(Cu /Fc) τ = 1.0 µs p • Ar Ar OMe P I O Cu O P Ar Me Ar O O O PCuIL ) = -2.4 V (vs Fc+ E1/2(CuII/I /Fc) τ = n.d • p Figure 2.2.1: CuI species observed during the catalytic reaction. Experiments showed that two CuI species were dominant during the course of the reaction. Specifically, the phenoxide complex PCuIOPh and the salicyclate complex PCuIL were present and theoretically could act as photocatalysts (Fig. 2.2.1). Stern-Volmer quenching experiments as well as luminescence decay measurements demonstrated that only PCuIOPh was quenched by the 302 PCuI(OPh), α-SOMO (–0.201 eV) PCuI(OPh), β-SOMO (–0.085 eV) PCuI(MSA), α-SOMO (–0.179 eV) PCuI(MSA), β-SOMO (–0.085 eV) Figure 2.1.3: Excited SOMOs of PCuIOPh (top) and PCuIL (bottom). electrophile, and it displayed a phosphorescence decay time on the order of τp = 1.0 μs, while the salicyclate complex showed no phosphorescence. Measurements indicated that the excited state reduction potential of each complex were similar. Therefore, the difference in reactivity was likely due to the differences in their excited state lifetimes, or their differing efficiency in undergoing intersystem crossing. To probe this difference, we turned to TD-DFT analysis to model the excited state of each complex. Figure 2.1.3 shows the predicted SOMOs of the triplet state for each complex. In the case of the LCuIOPh complex, the orbitals of the α and β SOMOs are widely distributed in space. This reduced overlap tends to increase the lifetime of the excited state. In 303 addition, the geometry of each complex likely plays a role. It has been reported that 4-coordinate CuI complexes can undergo rapid non-radiative decay via flattening of their tetrahedral geometry59. Given that PCuIOPh is Y shaped while PCuIL is tetrahedral, this relaxation pathway likely also plays a role in their divergent photoactivity. Figure 2.1.4 shows the geometric overlap between the excited triplet state and ground singlet state for the core region of each complex. The small change in geometry of the PCuIOPh complex limits non-radiative pathways for the excited state, increasing the lifetime. In contrat, PCuIL shows a flattening of the tetrahedral geometry around the Cu atom in the excited state, opening up a pathway for relaxation via geometric distortion of the Cu geometry. Figure 2.1.4: Geometric overlap between the ground state (blue) and excited state (red) for PCuIOPh (right) and PCuIL (left). 2.3: Computational investigations of the C—N coupling step We were also interested to study the nature of the C—N coupling step. EPR spectroscopy showed that the primary CuII species in solution was the species LCuII(morpholine)2OPh, when morpholine was used as the nucleophile. Using the alternative base cesium 2-phenylphenoxide, 304 (A) O N Me H Cu O O O H N O EPR comparison crystallographically characterized O Me N O H Cu O O H Cu O O OMe LCuII(NR2)2OAr (B) Me N O H N O O O H N O OMe LCuII(NR2)2OPh dominant CuII species O LCuINR2 OH N O OMe Figure 2.3.1 (A) Structure of the main copper paramagnet in solution (right), inferred from the crystallographically characterized LCuII(NR2)Oar (right). (B) Model reaction used for computational studies. the analogous complex LCuII(morpholine)2OAr was crystallographically characterized. The EPR spectrum of this new species matched that of the catalysis, allowing the structure of LCuII(morpholine)OPh to be assigned by analogy (Fig 2.3.1A). Since experimental results showed evidence that there was facile interconversion of CuII species, the immediate thermodynamic landscape around the main CuII species was calculated. The results of these calculations are summarized in Figure 2.3.2. In order for C-N coupling to occur, the phenoxide base must at some point serve as the terminal base to deprotonate the nucleophile. Starting from the primary CuII species 1 in the Figure, deprotonation and loss of phenol to yield intermediate 3 was found to be uphill by 17.5 kcal•mol-1, and thus not feasible under the reaction conditions. No evidence of any copper-amido species was found in experimental studies, consistent with this calculation. Loss of 305 O Me N O O H CuII O N O + PhOH PhOH N Me O LCu(NR2H)(NR2) (3) 17.5 O O Me O H O + O H N O - + O CuIII H N O O O OMe LCu(NR2H)2OPhR (1-R) 23.9 - O H N O O H N Me N O H CuIII O H CuII O O O OMe LCu(NR2H)OPh (2) 9.07 + - O N O + H N O O LCu(NR2H)2OPh (1) 0.00 - N CuII OMe OMe O H H N O O + PhOH PhOH O - O PhOH + PhOH N O H O CuIII O OMe OMe LCu(NR2H)2OPhR (2-R) 6.08 LCu(NR2)R (4-R) 21.9 Figure 2.3.2: Computational calculations of prospective CuII species. All values are ΔG values for 263.15K relative to species 1. one morpholine unit to form species was also found to be unfavorable by 9.07 kcal•mol-1, and therefore 2 is likely not a relevant species to C—N bond formation. Direct radical capture by 1 to generate species 1-R was found to be highly unfavorable, and uphill by 23.9 kcal•mol-1. In addition, during geometry optimization spontaneous dissociation of the phenoxide was noted. Likely, 1-R, to avoid being a 20-electron complex, is driven to dissociate a ligand to stabilize. Correspondingly, dissociation of a morpholine unit from 1-R to generate 2-R is much more favorable, relatively, being only 6.08 kcal•mol-1 uphill from 1. Deprotonation from this species to form 4-R is also not favorable and is not relevant to the reaction conditions. This analysis leaves two possibilities for C—N bond formation. Either the process occurs through an inner-sphere process from 2-R, or it occurs through species 1 via an outer-sphere process. In either case, deprotonation of the amine is likely to be synchronous with C—N bond formation. An extensive search of outer-sphere coupling mechanisms did not yield a transition state with an activation 306 (A) (B) Figure 2.3.3: (A) Calculated transition state for C—N bond formation from 2-R. (B) Calculated transition state A, but without phenol. energy of less than 30 kcal•mol-1 from 1. An inner-sphere reductive elimination from 2-R was lower in energy, and was the lowest transition state found in this study. After the initial optimization of the transition state, it was found that a phenol molecule was concurrently generated, and was loosely associated with the complex at the calculated transition state (Fig 2.3.3A). Recalculation of this transition state with the phenol removed, which provides a lowering of the activation energy by an increase in entropy, resulting in the transition state detailed in Figure 2.3.3B. The calculated energy barrier for this process is 24.5 kcal•mol-1 higher in energy relative to 1. While this energy barrier is still somewhat high for the reaction conditions, it is currently the best model for the C— N coupling step. 307 2.4: Computational details 2.4.1: General methods All calculations were performed using the Orca 5.0.3 software package.28–31 Geometry optimizations were performed using the B3LYP functional, utilizing the D4 dispersion correction.32–34 The def2-TZVP basis set was used for all atoms except copper where applicable, with which def2-QZVPPD was used.35,36 The RIJCOSX approximation was used with the def2/J auxiliary basis set in all calculations.37 Frequency calculations were performed to ensure that all molecular geometries were energy minima by confirming the absence of imaginary vibrational modes.38 All calculations included the implicit CPCM solvation model. A dielectric constant of 4.33 and a refractive index of 1.35 were chosen for the diethyl ether solvent, based on the literature.60 TD-DFT calculations were performed to estimate the excitation energies of PCuIOPh and PCuIL from their ground states. For both complexes, the number of roots was taken to be 20, and triplets were included. Transitions with energies greater than 350 nm were not considered, as they were deemed irrelevant to the reaction conditions (irradiation with 440 nm LED). For calculations of CuII species and organic molecules and fragments, the above options were using for geometry optimization, followed by an electronic energy optimization using the wB97M-V61 functional with the DEF2-TZVPD basis set, and the def2-QZFPPD basis set on copper. The SMD solvation model was used using diethyl ether as the option solvent.62 308 2.4.2: Calculated structures DTBM-SEGPHOS-CuOPh, singlet state Calculated geometry Cu1 P2 P3 C4 C5 H6 C7 H8 C9 H10 C11 O12 C13 C14 C15 H16 C17 C18 C19 H20 H21 H22 C23 Atom X 0 1.1952 1.5877 -2.2688 -3.1197 -2.7435 -4.4419 -5.1024 -4.896 -5.9219 -4.0529 -1.9292 -2.7064 0.2564 -1.0704 -1.4549 -1.923 -3.3338 -4.0912 -4.4215 -3.483 -4.9817 -4.1796 Y 0 1.4224 -1.346 -2.3239 -3.3484 -4.3653 -3.0879 -3.8898 -1.7704 -1.544 -0.7385 0.0171 -0.9816 2.1388 1.7562 1.0675 2.2314 1.6048 1.814 2.8366 1.5204 1.1818 2.1338 Z 0 1.2916 -0.8418 -0.486 -0.8758 -0.9043 -1.229 -1.5332 -1.1796 -1.4491 -0.7938 -0.0769 -0.4398 2.6726 2.7637 2.0252 3.7641 3.816 5.1385 5.2929 5.995 5.1259 2.6417 309 H24 H25 H26 C27 H28 H29 H30 C31 C32 H33 H34 H35 O36 C37 C38 C39 H40 H41 H42 C43 H44 H45 H46 C47 H48 H49 H50 C51 H52 C53 C54 H55 C56 C57 C58 H59 H60 H61 C62 H63 H64 H65 C66 -5.1648 -3.7035 -4.323 -3.1931 -2.5502 -2.7878 -4.1782 -1.3957 -2.9905 -2.3543 -3.4792 -3.7473 -2.2125 0.6202 -0.0158 0.3342 0.8049 0.7478 -0.7332 0.0997 0.6914 -0.9384 0.1955 2.1486 2.4434 2.612 2.5587 0.7798 1.8298 1.999 1.6772 1.0056 2.2071 1.8969 3.209 2.9792 3.8086 3.8036 1.0345 0.7154 1.5764 0.1385 1.1142 1.661 1.9079 3.2136 0.0717 -0.344 -0.2147 -0.3898 3.2059 4.9152 5.6126 5.4356 4.5208 3.8683 4.3835 3.5337 3.7209 4.2998 2.7101 3.6636 5.8335 6.4268 5.8936 6.2887 4.4594 4.97 3.4712 5.0254 2.992 3.2264 2.808 3.0114 2.3112 4.0678 4.1828 4.2419 4.2831 3.3489 5.114 5.4202 5.3865 6.3489 5.4375 2.9565 2.6483 1.6864 2.7017 3.6525 4.431 2.6839 3.7432 4.6254 4.9307 4.3824 5.7526 4.2524 5.5169 5.7574 4.6403 7.1206 7.9191 7.1484 7.3216 5.7651 6.4663 6.0771 4.777 5.602 4.6833 5.6099 6.4399 3.6418 3.6174 0.4322 -0.9025 -1.3737 -1.6341 -3.1397 -3.9476 -5.0152 -3.7679 -3.689 -3.4517 -4.4963 -3.3046 -2.8274 -3.6432 310 H67 H68 H69 C70 O71 C72 H73 H74 H75 C76 C77 C78 H79 H80 C81 H82 H83 H84 C85 H86 H87 H88 C89 H90 C91 C92 H93 C94 H95 C96 O97 O98 C99 C100 C101 C102 O103 O104 C105 C106 H107 C108 H109 0.1223 1.6451 0.9775 3.0435 3.4741 2.799 2.8051 3.3165 1.7685 3.4787 4.4953 5.567 5.1811 6.0366 3.7416 3.0457 3.1712 4.4507 5.2659 6.0518 5.7277 4.6319 2.9249 3.2346 3.0774 3.3868 2.8145 4.4138 4.6355 5.1211 6.1438 5.682 4.8347 3.8148 3.6476 4.6441 5.7823 5.7129 4.6019 3.5469 3.4969 2.543 1.7137 2.8867 2.0238 3.0473 4.9747 6.085 7.3174 7.889 7.8936 7.1445 4.7398 5.6039 6.2573 7.0524 5.5199 6.6834 6.2181 7.355 7.2845 4.7387 5.3453 3.8724 4.3843 3.6427 3.4262 -0.3708 -0.1296 -0.6256 0.735 0.9127 1.3396 2.2445 1.8278 1.0974 0.2736 0.0496 -0.637 -1.1689 -1.6683 -0.9409 -0.5567 -0.8019 0.1902 0.5332 -3.1928 -3.4512 -4.7219 -0.9444 -1.6398 -1.3789 -2.3065 -0.6112 -1.066 0.3779 1.1572 0.2633 -0.3649 -0.3897 1.9607 2.6612 1.3222 2.5357 2.18 2.6325 1.7069 2.9922 1.0353 2.0437 -1.2413 -2.5776 -3.3476 -2.9707 -4.0136 -1.9646 -2.0595 0.1577 -0.6307 -0.2118 1.2475 1.9025 1.3532 3.5942 3.2542 4.0405 5.0923 3.4134 4.0136 311 C110 C111 C112 H113 C114 C115 C116 H117 H118 H119 C120 H121 H122 H123 C124 H125 H126 H127 C128 O129 C130 H131 H132 H133 C134 C135 C136 H137 H138 H139 C140 H141 H142 H143 C144 H145 H146 H147 C148 H149 C150 C151 H152 2.5794 1.1863 0.1577 -0.3329 -0.2656 -1.3099 -2.6831 -2.6329 -3.0623 -3.4088 -0.8667 -1.5662 0.1291 -0.8502 -1.4474 -1.9254 -0.4773 -2.0648 0.3226 -0.1805 -1.3699 -1.2221 -1.5808 -2.2151 1.4495 2.2604 2.7536 3.3524 3.3823 1.923 1.4436 2.1047 0.6564 0.9944 3.5055 3.2442 4.1605 4.0755 1.8539 2.6939 2.0946 3.2683 3.9835 0.5122 -2.2429 -1.7266 -0.8276 -2.3246 -1.5491 -1.6098 -1.2203 -2.6304 -1.0121 -0.0677 0.487 0.02 0.4168 -2.008 -2.9768 -2.0512 -1.2794 -3.5599 -4.3259 -5.0463 -5.6406 -5.7052 -4.3757 -4.0631 -5.2729 -4.9932 -5.8352 -4.1 -4.8478 -6.579 -7.423 -6.5825 -6.7421 -5.5111 -5.7766 -4.6385 -6.3411 -3.38 -3.7424 -2.6068 -3.3457 -3.0984 2.0596 -2.3678 -3.1354 -2.7906 -4.3236 -5.156 -4.4617 -3.4446 -4.4038 -5.0189 -5.2268 -5.8551 -5.6667 -4.2524 -6.6182 -6.7247 -7.115 -7.1482 -4.6445 -5.6743 -5.3381 -4.4344 -6.1787 -5.1836 -3.9493 -4.4516 -5.8858 -6.2419 -5.9067 -6.5729 -4.429 -4.6398 -5.1765 -3.4469 -3.5804 -2.5544 -3.5523 -4.0011 -2.8102 -2.2432 0.3587 0.2782 -0.4892 312 C153 C154 C155 H156 H157 C158 H159 H160 H161 C162 H163 H164 C165 O166 C167 H168 H169 H170 C171 C172 C173 H174 H175 H176 C177 H178 H179 H180 C181 H182 H183 H184 C185 H186 H187 C188 C189 H190 H191 H192 H193 H194 H195 3.5316 4.8436 5.7874 6.0141 5.3748 4.5685 3.9889 4.0322 5.5164 5.5967 5.0476 5.7604 2.5611 2.7843 1.9991 1.6616 1.1336 2.6329 1.4428 0.443 -0.7642 -1.4824 -0.4773 -1.2705 1.0789 1.9736 1.3573 0.3629 -0.1037 -0.7279 0.7047 -0.7266 1.2258 0.354 6.3437 6.6703 6.5965 7.0962 7.3086 6.5716 6.8444 7.5867 6.725 -4.3876 -5.1861 -4.5457 -3.5065 -4.5818 -6.6238 -6.6179 -7.2108 -7.1294 -5.223 -5.78 -4.2146 -4.666 -5.7634 -6.9302 -6.9594 -6.9723 -7.794 -3.8359 -3.9296 -4.797 -4.8482 -5.814 -4.3601 -4.4567 -3.8831 -5.5039 -4.3361 -2.5251 -2.1075 -1.823 -2.5985 -2.84 -2.2103 6.6848 2.3596 -1.5257 -2.47 -0.7185 -5.6963 3.407 1.766 -5.1039 1.1594 1.0303 -0.0031 0.2363 -1.0128 0.5486 -0.3766 1.2875 0.348 2.3754 3.1291 2.7566 2.1528 2.9555 2.7005 1.6635 3.3626 2.9 2.3606 3.5332 3.1244 3.9467 2.8641 2.2612 4.8331 5.0845 4.7889 5.6486 3.8764 3.088 4.081 4.7693 1.4105 1.4954 0.9006 -0.7313 2.4742 2.2778 2.6768 2.2362 -0.4985 -0.6516 -0.0133 313 H196 H197 -1.2436 -4.4122 -2.5433 0.2838 -0.2177 -0.7621 DTBM-SEGPHOS-CuOPh, triplet state Calculated geometry Cu1 P2 P3 C4 C5 H6 C7 H8 C9 H10 C11 O12 C13 C14 C15 H16 C17 C18 C19 H20 H21 Atom X 0 1.3251 1.6208 -2.6528 -3.7687 -3.6553 -5.0257 -5.8956 -5.1462 -6.1174 -4.0351 -1.7158 -2.7627 0.253 -1.0363 -1.3539 -1.942 -3.3039 -4.1124 -4.5257 -3.5099 Y 0 1.0897 -1.4374 -1.8675 -2.6568 -3.5934 -2.2572 -2.8747 -1.0529 -0.7309 -0.2599 0.1287 -0.6474 1.7051 1.2099 0.4436 1.663 0.936 1.1788 2.18 0.9952 Z 0 1.4625 -0.6128 0.2309 0.4625 0.9957 0.0156 0.1986 -0.6758 -1.0328 -0.9179 -0.7 -0.4602 2.7867 2.8878 2.1962 3.8493 3.9195 5.2061 5.2768 6.0963 314 H22 C23 H24 H25 H26 C27 H28 H29 H30 C31 C32 H33 H34 H35 O36 C37 C38 C39 H40 H41 H42 C43 H44 H45 H46 C47 H48 H49 H50 C51 H52 C53 C54 H55 C56 C57 C58 H59 H60 H61 C62 H63 H64 -4.9508 -4.1588 -5.1031 -3.6483 -4.3888 -3.0457 -2.4174 -2.5706 -3.9982 -1.5086 -3.2257 -2.6207 -3.791 -3.9168 -2.3962 0.3868 -0.1612 0.1149 0.5255 0.5975 -0.9503 -0.2325 0.3017 -1.2789 -0.1466 1.9093 2.188 2.4369 2.2628 0.6907 1.7158 2.1657 1.8417 1.1162 2.4514 2.1461 3.4551 3.2254 3.9713 4.1271 1.3988 1.0794 2.0211 0.4789 1.3167 0.7674 1.0707 2.3831 -0.5879 -0.897 -0.9135 -1.1158 2.7224 4.3262 5.0491 4.8384 3.8451 3.3689 4.0992 3.1566 3.4801 4.1269 2.5037 3.357 5.5079 6.1732 5.5101 5.9217 4.2723 4.7679 3.3183 4.8952 2.6431 2.9698 2.5024 2.8516 2.2507 3.9222 4.1922 4.1973 4.3438 3.2417 4.9892 5.5248 5.6151 6.3844 5.2171 2.6955 2.7139 1.7642 2.682 3.8771 4.7141 2.9547 3.952 4.666 4.8327 4.2823 5.6092 4.1401 5.4977 5.7757 4.6873 7.1622 7.9415 7.246 7.3443 5.7036 6.386 5.9932 4.6965 5.6475 4.7163 5.7007 6.4707 3.7191 3.6851 0.6785 -0.6222 -1.1487 -1.2652 -2.7515 -3.5669 -4.6253 -3.4637 -3.2472 -2.9449 -3.986 -2.7172 315 H65 C66 H67 H68 H69 C70 O71 C72 H73 H74 H75 C76 C77 C78 H79 H80 C81 H82 H83 H84 C85 H86 H87 H88 C89 H90 C91 C92 H93 C94 H95 C96 O97 O98 C99 C100 C101 C102 O103 O104 C105 C106 H107 0.507 1.2536 0.2639 1.7058 1.1155 3.3671 3.8933 3.3542 3.3522 3.9745 2.3347 3.7906 4.9006 6.0337 5.7371 6.4061 4.2846 3.5476 3.7894 5.0642 5.573 6.421 5.9359 4.9047 3.1546 3.4553 3.0815 3.3208 2.633 4.4173 4.592 5.2811 6.3635 6.0025 5.0637 3.9564 3.8032 4.8513 6.0391 5.9117 4.7728 3.6248 3.5623 5.5653 3.0883 3.0639 2.1008 3.2877 4.6915 5.8101 7.0804 7.7033 7.5617 6.9831 4.3079 5.0029 5.5748 6.4414 4.8212 6.1141 5.6915 6.8834 6.5947 3.9964 4.4856 3.118 3.6644 3.2056 2.8621 -0.5009 -0.2234 -0.6117 0.5059 0.7079 0.9483 1.7873 1.3725 0.693 0.0032 -0.1829 -0.7159 -1.2124 -1.669 -1.003 -0.7634 -1.0024 -2.3154 -3.3469 -2.8867 -3.2474 -4.4109 -0.5125 -1.1223 -0.7525 -1.6466 0.0044 -0.3769 0.7793 1.5991 0.7254 0.1447 0.0295 2.4725 3.1571 1.8843 3.0694 2.5594 3.0416 2.0265 3.3536 1.3458 2.3221 -1.031 -2.3838 -3.1218 -2.825 -3.8713 -1.8269 -1.9722 0.2533 -0.4957 0.0042 1.4345 2.1839 1.6842 3.9263 3.5245 4.2739 5.3256 316 C108 H109 C110 C111 C112 H113 C114 C115 C116 H117 H118 H119 C120 H121 H122 H123 C124 H125 H126 H127 C128 O129 C130 H131 H132 H133 C134 C135 C136 H137 H138 H139 C140 H141 H142 H143 C144 H145 H146 H147 C148 H149 C150 2.577 1.6838 2.645 1.1318 -0.0962 -0.7208 -0.5458 -1.8834 -3.063 -3.0035 -3.0887 -4.0077 -1.9578 -2.8658 -1.102 -1.9978 -2.0545 -2.2152 -1.1863 -2.9265 0.2756 -0.1534 -1.053 -0.7111 -1.067 -2.0619 1.5834 2.5833 2.7947 3.5204 3.1865 1.867 2.1127 2.9247 1.2609 1.8459 3.9562 3.9062 4.3857 4.6421 1.9759 2.9539 2.0734 -0.1603 0.0962 0.1614 -2.3904 -2.1642 -1.3791 -2.9142 -2.4833 -2.9974 -2.6197 -4.0859 -2.6564 -0.9378 -0.6345 -0.5136 -0.4979 -2.928 -3.9949 -2.6508 -2.4182 -3.9788 -4.8687 -5.8791 -6.3027 -6.656 -5.4883 -4.168 -5.1664 -4.819 -5.507 -3.8045 -4.8909 -6.6276 -7.2963 -6.8442 -6.8606 -5.079 -5.3658 -4.0777 -5.7665 -3.3647 -3.4907 -2.6773 3.5873 4.138 2.228 -2.0735 -2.667 -2.2722 -3.7577 -4.4002 -3.5517 -2.5311 -3.5055 -3.9824 -4.4239 -4.9482 -4.9536 -3.4296 -5.8642 -5.9787 -6.4644 -6.2794 -4.1714 -5.1318 -4.6684 -3.7225 -5.4311 -4.5391 -3.6595 -4.2744 -5.7619 -6.2027 -5.8653 -6.3254 -4.142 -4.4369 -4.7787 -3.1088 -3.5857 -2.5334 -3.6491 -4.0831 -2.5997 -2.1681 0.6301 317 C151 H152 C153 C154 C155 H156 H157 C158 H159 H160 H161 C162 H163 H164 C165 O166 C167 H168 H169 H170 C171 C172 C173 H174 H175 H176 C177 H178 H179 H180 C181 H182 H183 H184 C185 H186 H187 C188 C189 H190 H191 H192 H193 3.2746 4.0154 3.5243 4.8868 5.8477 5.9983 5.4951 4.7589 4.2015 4.2701 5.7559 5.5369 4.9409 5.6507 2.5049 2.6693 1.8825 2.066 0.8168 2.1854 1.3698 0.3422 -1.0013 -1.7427 -0.9055 -1.3867 0.7757 1.7639 0.7885 0.062 0.1198 -0.2622 1.0514 -0.608 1.1635 0.2716 6.861 6.9988 6.8267 7.4147 7.4587 6.5287 7.3734 -3.3745 -3.0579 -4.4612 -5.1779 -4.4741 -3.4261 -4.5289 -6.6373 -6.6948 -7.2687 -7.0473 -5.1438 -5.6871 -4.1165 -4.8323 -6.0147 -7.0959 -7.2461 -6.9227 -7.9845 -4.0348 -4.1798 -4.6778 -4.745 -5.6647 -3.9951 -5.0878 -4.8142 -6.1432 -4.9581 -2.7851 -2.0538 -2.3973 -2.8674 -2.9865 -2.3827 5.8736 1.7592 -1.4742 -2.3763 -0.6036 -5.6009 2.7496 0.5614 -0.1547 1.387 1.3326 0.3594 0.617 -0.6726 0.8549 -0.0827 1.5906 0.6767 2.7305 3.4604 3.0787 2.2985 2.9886 2.4829 1.4173 2.6351 3.0342 2.5203 3.6645 3.0983 3.8983 2.643 2.3398 4.8283 5.1986 4.5739 5.645 4.2931 3.5843 4.7064 5.1026 1.6213 1.7067 1.3723 -0.6894 2.8432 2.6923 3.0585 2.6875 -0.4434 318 H194 H195 H196 H197 7.8001 6.8163 -1.6741 -4.1268 1.0098 -4.9755 -2.187 0.6753 -0.7019 0.402 0.5674 -1.4565 DTBM-SEGPHOS-L, singlet state Calculated geometry Cu1 P2 O3 P4 C5 H6 H7 H8 O9 C10 C11 C12 H13 C14 H15 C16 H17 C18 C19 Atom X 0 1.1621 -1.5855 1.6457 -2.8755 -1.9111 -3.5847 -2.7501 -3.4497 -3.3736 -2.7054 -4.7416 -5.2382 -5.4476 -6.4965 -4.7899 -5.3461 -3.4594 -2.7732 Y 0 1.4247 -1.2136 -1.3283 -3.3428 -3.704 -4.1632 -2.8701 -2.4222 -0.4557 -1.3489 -0.6735 -1.5075 0.1514 -0.0281 1.2462 1.9128 1.5036 2.684 Z 0 1.3191 0.8196 -0.7812 1.6008 1.2466 1.672 2.5738 0.6643 -0.6082 0.3256 -0.8857 -0.4124 -1.7239 -1.9203 -2.3105 -2.9618 -2.082 -2.7005 319 H20 H21 H22 O23 C24 C25 C26 H27 C28 C29 C30 H31 H32 H33 C34 H35 H36 H37 C38 H39 H40 H41 C42 C43 H44 H45 H46 O47 C48 C49 C50 H51 H52 H53 C54 H55 H56 H57 C58 H59 H60 H61 C62 -2.3375 -3.4737 -1.947 -1.4299 -2.6821 0.1839 -1.0734 -1.3783 -1.9531 -3.2633 -4.0348 -4.5036 -3.3879 -4.8297 -4.1853 -5.0942 -3.6958 -4.4797 -2.9081 -2.223 -2.4502 -3.8196 -1.5397 -3.3387 -2.8082 -3.8974 -4.0306 -2.4198 0.3262 -0.2189 0.1814 0.5888 0.7358 -0.8603 -0.3934 0.1363 -1.4162 -0.4024 1.8222 2.0099 2.4207 2.177 0.6146 3.3312 3.2723 2.3764 0.8932 0.6389 2.2668 1.7453 0.8715 2.3068 1.5301 1.943 2.9192 1.945 1.213 1.6488 1.0623 1.276 2.6832 0.0364 -0.0907 -0.4096 -0.5245 3.5031 5.023 5.6775 5.6246 4.3983 4.2341 5.1484 4.0008 4.7633 5.5582 3.8466 4.6092 6.4853 7.2883 6.4772 6.7235 5.3889 5.7225 4.495 6.171 3.3644 -1.935 -3.2947 -3.3446 -1.1062 -1.2324 2.598 2.8435 2.2871 3.7715 4.0279 5.2929 5.2151 6.1707 5.4617 2.7986 2.9547 1.8979 2.6152 4.2253 5.0663 3.3453 4.4416 4.3797 4.3892 3.695 5.1041 3.8238 5.1502 5.1184 4.2465 6.6049 7.2348 6.8185 6.8781 4.8572 5.3753 5.2212 3.7914 4.8535 3.8312 5.0376 5.5266 3.3373 320 H63 C64 C65 H66 C67 C68 C69 H70 H71 H72 C73 H74 H75 H76 C77 H78 H79 H80 C81 O82 C83 H84 H85 H86 C87 C88 C89 H90 H91 C92 H93 H94 H95 C96 H97 H98 H99 C100 H101 C102 C103 H104 C105 1.6172 1.9995 1.5734 0.8058 2.1148 1.6529 2.7583 2.4221 3.6719 3.0099 0.399 0.0486 0.5853 -0.4047 1.2643 0.3852 2.0836 1.0298 3.0524 3.5433 2.7109 2.2473 3.3475 1.9332 3.5801 4.7082 5.9033 5.6562 6.2289 4.1834 3.3304 3.8787 4.9691 5.2437 6.0772 5.6036 4.4895 3.0362 3.4226 3.162 3.5656 3.0038 4.6814 3.7279 2.7469 2.9809 2.3391 3.993 4.0822 4.5845 4.4563 4.0003 5.6303 4.9712 4.9953 5.9956 4.5703 2.68 2.272 1.9715 2.7517 4.8439 5.9485 7.1069 7.1885 7.9779 7.0833 4.5776 5.417 5.5687 6.184 4.5963 6.8088 6.7184 7.399 7.3616 4.7557 5.35 3.7426 4.7149 3.5117 3.2639 -0.3425 -0.0246 -0.4144 0.775 3.1893 0.396 -0.9008 -1.3038 -1.6938 -3.1647 -4.1131 -5.1442 -3.9832 -3.973 -3.2745 -4.3097 -2.9595 -2.6557 -3.6846 -3.1904 -3.563 -4.7481 -1.0764 -1.7382 -1.8094 -2.7934 -1.6515 -1.0449 0.2094 0.8414 -0.1216 -0.9813 -0.492 1.2433 1.9192 0.3842 1.7647 2.1245 2.5027 1.9425 2.912 0.9157 1.8908 -1.0466 -2.3411 -3.1768 -2.6129 321 H106 C107 O108 O109 C110 C111 C112 C113 O114 O115 C116 C117 H118 C119 H120 C121 C122 C123 H124 C125 C126 C127 H128 H129 H130 C131 H132 H133 H134 C135 H136 H137 H138 C139 O140 C141 H142 H143 H144 C145 C146 C147 H148 4.9726 5.392 6.5148 5.8601 4.9964 3.8746 3.5684 4.4562 5.5642 5.3226 4.3177 3.2828 3.1709 2.3741 1.549 2.4929 1.3201 0.1191 -0.5223 -0.2803 -1.5657 -2.7942 -2.7104 -2.9199 -3.6995 -1.4675 -2.3602 -0.5961 -1.3969 -1.7868 -2.0514 -0.9049 -2.6132 0.5528 0.138 -0.7824 -0.3608 -0.9625 -1.7262 1.8469 2.877 3.0847 3.8362 1.0151 1.2183 2.0061 1.5072 0.9165 0.1766 -0.0312 -0.7659 -1.4344 -1.7825 -0.9669 -0.41 -0.5559 0.361 0.8163 0.561 -2.1356 -1.8124 -1.0961 -2.3644 -1.7859 -2.2255 -1.9113 -3.3095 -1.7734 -0.2432 0.1923 0.1075 0.1382 -2.1331 -3.1729 -1.9048 -1.5231 -3.3557 -4.1034 -5.1445 -5.8054 -5.7073 -4.7414 -3.6158 -4.4794 -3.9025 -4.491 -3.6261 -1.5276 -1.4902 0.6526 -0.2345 0.066 1.5053 2.2581 1.8098 4.0718 3.6219 4.3265 5.3916 3.5934 4.1212 2.2207 -2.3811 -2.9887 -2.4955 -4.21 -4.841 -4.0223 -2.982 -4.0398 -4.4343 -4.7851 -5.238 -5.3427 -3.7703 -6.3231 -6.4904 -6.9224 -6.6946 -4.75 -5.8318 -5.4952 -4.7351 -6.4096 -5.1266 -4.2337 -4.9864 -6.4018 -6.9341 322 H149 H150 C151 H152 H153 H154 C155 H156 H157 H158 C159 H160 C161 C162 H163 C164 C165 C166 H167 H168 C169 H170 H171 H172 C173 H174 H175 C176 O177 C178 H179 H180 H181 C182 C183 C184 H185 H186 H187 C188 H189 H190 H191 3.4421 2.1637 2.4457 3.2696 1.5905 2.197 4.2452 4.2055 4.6391 4.9549 2.194 3.1665 2.1919 3.3161 3.931 3.6887 4.9488 5.9509 6.1941 5.5833 4.5527 4.0846 3.853 5.4414 5.717 5.2009 5.901 2.8633 3.112 2.6151 1.7818 2.2756 3.4035 1.8011 1.0251 0.1031 -0.5194 0.6603 -0.5592 1.9924 2.6477 2.6108 1.4172 -2.8717 -3.9181 -5.9551 -6.5482 -6.0886 -6.3547 -4.4579 -4.9096 -3.4448 -5.0341 -2.9965 -3.1781 -2.6397 -3.4187 -3.2048 -4.4536 -5.2707 -4.3996 -3.4816 -4.1298 -6.4457 -6.074 -7.1279 -7.0163 -5.794 -6.5912 -4.993 -4.6791 -5.7363 -7.0197 -6.9301 -7.5208 -7.6211 -3.8116 -3.9041 -5.1376 -5.116 -6.0698 -5.14 -3.9531 -3.0812 -4.8458 -3.9384 -6.3455 -6.9799 -5.0835 -5.4877 -5.7391 -4.0979 -4.2844 -3.2919 -4.1852 -4.8804 -3.0424 -2.6202 0.3613 0.1389 -0.7183 0.994 0.6333 -0.1566 0.3786 -1.1461 -0.2838 -1.1969 0.1945 -0.5661 1.8623 2.3858 2.58 2.116 2.9658 2.5836 1.8855 3.49 2.1283 2.4541 3.7836 3.8031 4.7012 3.8114 2.9348 4.9837 4.9823 4.9745 5.9127 323 C192 H193 H194 H195 C196 H197 H198 C199 C200 H201 H202 H203 H204 H205 H206 0.1312 -0.6541 0.7077 -0.3516 1.4684 0.6361 6.7417 6.9848 6.2591 6.6006 7.0893 6.6841 7.3597 7.7511 6.8709 -2.6681 -2.5926 -1.7441 -2.7436 -2.8243 -2.1669 6.0295 1.8945 -1.852 -2.8766 -1.1648 -6.1815 2.8552 1.1131 -4.9676 3.99 3.2407 3.9701 4.966 1.5319 1.7227 0.4061 -0.1407 2.9888 2.8672 3.183 1.5353 0.1999 -0.0891 -0.3035 DTBM-SEGPHOS-L, triplet state Calculated geometry Cu1 P2 O3 P4 C5 Atom X 0 1.2393 -1.2776 1.7724 -2.6275 Y 0 1.4657 -1.4587 -1.2682 -3.6614 Z 0 1.2421 0.0449 -0.7431 -0.0597 324 H6 H7 H8 O9 C10 C11 C12 H13 C14 H15 C16 H17 C18 C19 H20 H21 H22 O23 C24 C25 C26 H27 C28 C29 C30 H31 H32 H33 C34 H35 H36 H37 C38 H39 H40 H41 C42 C43 H44 H45 H46 O47 C48 -1.9282 -3.3958 -2.0761 -3.3204 -3.2566 -2.5492 -4.687 -5.2106 -5.3991 -6.4832 -4.7392 -5.3015 -3.3339 -2.6076 -1.8701 -3.3099 -2.0578 -1.2756 -2.5884 0.1241 -0.933 -0.997 -1.9226 -2.9379 -3.7735 -4.5182 -3.1426 -4.3054 -3.8753 -4.5632 -3.3192 -4.4676 -2.1421 -1.4342 -1.5885 -2.8347 -1.8767 -4.0498 -3.7332 -4.7732 -4.5092 -2.9422 -0.5814 -3.7957 -4.4318 -3.743 -2.4231 -0.0676 -1.2756 -0.0574 -1.0023 1.1256 1.094 2.3564 3.2825 2.4004 3.7169 3.79 4.5462 3.8537 1.3247 1.2184 2.3394 1.6303 0.5672 2.2434 1.3118 1.9714 2.6664 2.5005 1.1835 0.6765 -0.0153 0.1215 1.4257 0.1812 0.5916 -0.4362 -0.4725 3.648 4.4684 4.9086 5.1211 3.5011 4.349 5.889 -0.8878 -0.1015 0.8791 -0.1576 -0.2451 -0.1296 -0.2626 -0.2548 -0.2477 -0.2396 -0.2271 -0.1974 -0.2675 -0.3011 0.5013 -0.2001 -1.2369 -0.4861 -0.3194 2.3614 2.908 2.7225 3.6736 4.3711 5.4819 5.1065 6.1971 6.02 3.3291 3.8218 2.5737 2.8041 5.0658 5.7894 4.3615 5.5995 3.7482 3.3655 2.4193 3.8508 3.1632 4.2668 3.6083 325 C49 C50 H51 H52 H53 C54 H55 H56 H57 C58 H59 H60 H61 C62 H63 C64 C65 H66 C67 C68 C69 H70 H71 H72 C73 H74 H75 H76 C77 H78 H79 H80 C81 O82 C83 H84 H85 H86 C87 C88 C89 H90 H91 -0.7563 -0.6327 -0.4916 0.1649 -1.5865 -1.6575 -1.3951 -2.6382 -1.7206 0.7837 0.8808 1.6135 0.8875 0.231 1.0804 2.0945 1.6742 0.8992 2.2159 1.7561 2.8161 2.4917 3.777 2.975 0.4343 0.0997 0.53 -0.3434 1.4826 0.6398 2.3581 1.2414 3.1407 3.6107 2.7337 2.14 3.3609 2.0669 3.6659 4.8049 6.018 5.7872 6.3415 4.389 6.1095 7.1693 5.5502 5.7937 6.752 7.8076 6.6102 6.5241 6.4013 6.3403 5.8525 7.4502 3.7017 4.2363 2.7244 2.9303 2.2922 3.9315 3.9861 4.571 4.4022 4.0705 5.6367 4.7704 4.7921 5.7984 4.2891 2.5541 2.078 1.9163 2.6012 4.7994 5.91 7.0375 7.0185 7.9282 7.0704 4.5553 5.3961 5.4267 5.9426 4.4155 3.3076 5.1336 5.3597 5.6282 5.5505 2.9216 3.0253 3.3653 1.8557 3.1182 2.0325 3.5672 3.4008 2.6133 2.2244 0.2785 -1.0235 -1.4161 -1.8282 -3.3014 -4.2536 -5.2825 -4.1182 -4.1294 -3.4121 -4.4523 -3.0671 -2.8169 -3.8153 -3.3182 -3.6922 -4.8785 -1.2159 -1.8799 -1.9499 -2.8638 -1.9577 -1.0873 0.0764 0.6843 -0.2671 -1.1951 -0.5156 326 C92 H93 H94 H95 C96 H97 H98 H99 C100 H101 C102 C103 H104 C105 H106 C107 O108 O109 C110 C111 C112 C113 O114 O115 C116 C117 H118 C119 H120 C121 C122 C123 H124 C125 C126 C127 H128 H129 H130 C131 H132 H133 H134 4.3404 3.4428 4.1328 5.1256 5.2849 6.1305 5.6116 4.5086 3.1218 3.4842 3.3089 3.779 3.2385 4.9397 5.2887 5.6168 6.7638 5.9864 5.15 3.9874 3.568 4.3429 5.4483 4.9686 4.0609 2.9936 2.7741 2.199 1.3516 2.4599 1.3393 0.1266 -0.481 -0.3502 -1.6917 -2.8614 -2.7921 -2.8859 -3.8105 -1.7654 -2.6695 -0.9067 -1.8195 6.835 6.8329 7.397 7.3645 4.8011 5.3886 3.7662 4.8392 3.5016 3.2829 -0.3237 -0.009 -0.3627 0.7447 0.9876 1.1416 1.8805 1.3966 0.844 0.1478 -0.0626 -0.8572 -1.5738 -1.9555 -1.0794 -0.4819 -0.6456 0.3516 0.8396 0.568 -1.9396 -1.5469 -0.8507 -2.0307 -1.451 -2.1491 -2.0041 -3.221 -1.7231 0.0541 0.4754 0.595 0.2405 0.9821 1.6035 0.0772 1.5275 2.0196 2.3806 1.9155 2.7863 0.7994 1.791 -0.9494 -2.2203 -3.0853 -2.4257 -3.4196 -1.3013 -1.2051 0.903 -0.0294 0.2041 1.612 2.4245 2.0646 4.2867 3.7639 4.3834 5.4289 3.5905 4.0489 2.2397 -2.3692 -2.9083 -2.3557 -4.1272 -4.6283 -3.9061 -2.8275 -4.1011 -4.2404 -4.2769 -4.7193 -4.6788 -3.2057 327 C135 H136 H137 H138 C139 O140 C141 H142 H143 H144 C145 C146 C147 H148 H149 H150 C151 H152 H153 H154 C155 H156 H157 H158 C159 H160 C161 C162 H163 C164 C165 C166 H167 H168 C169 H170 H171 H172 C173 H174 H175 C176 O177 -1.8799 -2.0361 -1.0195 -2.7586 0.4428 -0.0049 -0.9253 -0.6104 -0.9284 -1.933 1.7451 2.7237 2.9285 3.643 3.3323 1.9968 2.2326 3.0281 1.3664 1.9793 4.1052 4.0646 4.5447 4.7775 2.1536 3.1254 2.2188 3.3383 3.9924 3.6519 4.9275 5.9952 6.2029 5.7083 4.5921 4.2066 3.8452 5.4931 5.5975 5.0348 5.7464 2.7606 2.9392 -1.5334 -2.5428 -1.1142 -0.9452 -2.9984 -3.6408 -4.7124 -5.3254 -5.3162 -4.3409 -3.3294 -4.1783 -3.51 -4.0901 -2.5022 -3.4441 -5.6262 -6.2216 -5.6843 -6.0817 -4.2618 -4.7814 -3.2757 -4.8233 -2.8017 -3.0549 -2.6553 -3.4378 -3.1789 -4.5351 -5.3333 -4.3957 -3.5478 -4.0101 -6.3916 -5.9116 -7.1056 -6.948 -6.0033 -6.8403 -5.2891 -4.8268 -5.9483 -6.1538 -6.5195 -6.6787 -6.4261 -4.7686 -5.9013 -5.675 -4.8289 -6.581 -5.4906 -4.3145 -5.1493 -6.5244 -7.1136 -6.4025 -7.0813 -5.3389 -5.793 -5.9902 -4.3791 -4.4781 -3.5191 -4.3174 -5.1286 -3.0982 -2.7109 0.33 0.1009 -0.7151 0.9008 0.5501 -0.0586 0.5937 -1.0364 -0.5203 -1.4214 -0.1785 -0.7913 1.7648 2.1629 2.5762 1.9557 2.7361 328 C178 H179 H180 H181 C182 C183 C184 H185 H186 H187 C188 H189 H190 H191 C192 H193 H194 H195 C196 H197 H198 C199 C200 H201 H202 H203 H204 H205 H206 2.4543 1.5999 2.1481 3.2363 1.6902 0.8452 -0.0286 -0.7145 0.5602 -0.6271 1.7632 2.356 2.441 1.1536 -0.1085 -0.8604 0.4281 -0.6357 1.4266 0.5902 6.8512 7.156 5.9804 6.1988 6.8695 6.5779 7.509 7.9184 6.9195 -7.1851 -7.0235 -7.7969 -7.7121 -3.9689 -4.1396 -5.4066 -5.4129 -6.3173 -5.4252 -4.1894 -3.2766 -5.0384 -4.2679 -2.948 -2.8839 -1.9997 -3.0744 -2.9075 -2.2555 5.9414 1.7788 -2.1113 -3.1679 -1.5435 -6.3767 2.7439 0.9998 -4.9585 2.2069 1.5483 3.0545 1.6594 2.2974 3.5747 3.5174 4.3679 3.5645 2.6041 4.8128 4.8866 4.7798 5.7162 3.7719 2.9837 3.8124 4.7187 1.441 1.6297 0.2174 0.1712 3.2816 3.1473 3.5711 1.4624 0.5239 0.2726 -0.1979 329 LCu(NR2H)2OPh (1) Calculated geometry Cu1 O2 O3 O4 O5 O6 O7 N8 N9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 Atom X 0 2.3161 -1.3023 1.3337 -1.2042 -3.0256 -2.8008 1.3171 -0.9489 3.5937 -2.9905 -3.0807 -2.3675 2.2451 -2.3505 1.9901 2.9643 -4.2625 0.7213 1.7395 4.5612 -4.9261 1.9228 -2.3517 -0.814 -2.4375 -1.4385 Y 0 1.4975 1.7641 -0.0035 -0.401 3.1429 -3.4952 0.9234 -1.4097 0.598 1.2286 -0.6483 0.0642 0.9406 2.0223 -0.1025 0.5267 1.6283 1.9725 2.5324 1.5766 0.9264 2.3143 -1.1261 -2.7786 -1.8682 -3.8085 Z 0 -3.9562 0.3892 1.4188 -1.4736 0.1176 1.8746 -1.3307 1.2103 1.8121 -1.2425 -2.8176 -1.7975 1.5827 -0.1983 -2.1564 -3.1402 -1.7089 -2.1835 -3.1637 1.9912 -2.6838 1.5347 1.5697 0.6716 -3.409 1.6005 330 C28 C29 C30 C31 C32 H33 H34 H35 H36 H37 H38 H39 H40 H41 H42 H43 H44 H45 H46 H47 H48 H49 H50 H51 H52 H53 H54 H55 H56 H57 H58 H59 H60 H61 H62 H63 H64 -4.3193 -2.9232 4.2287 2.9022 -2.4589 2.0135 1.2161 2.5148 3.7947 3.3728 -4.7175 0.3365 -0.1148 1.2624 2.5336 5.5891 -5.9023 0.8919 -2.9303 -2.3985 0.2455 -1.307 -1.4759 -3.0822 -2.23 -1.4283 -0.8751 -4.8375 -2.4055 -3.9866 4.9878 2.6242 -1.4728 -2.3779 -3.1462 -0.3629 3.8575 -0.2141 -2.2077 2.9293 3.2846 3.9654 1.3625 -0.6536 -0.7934 0.998 -0.2292 2.5069 2.7646 1.5283 3.2289 3.0649 1.2809 1.2454 2.597 -1.0717 -0.1547 -2.9945 -2.7994 -1.6265 -2.3156 -2.6185 -4.7964 -3.8562 -0.7742 -2.2019 -2.04 3.689 4.3318 4.3233 3.4095 4.7993 -1.3193 -0.4526 -3.2318 2.4728 1.9369 1.7063 1.1497 -0.7296 -2.6928 -1.495 -2.5957 -3.8114 -1.2765 -1.5417 -2.7221 -3.8536 -2.6212 2.169 -3.0242 1.3596 0.6472 2.0614 0.5257 -0.3009 -3.8697 -4.166 -2.6416 1.1393 2.5433 -4.0031 3.4425 2.6453 2.0718 1.6631 0.8558 2.0831 1.2627 2.038 1.8475 331 LCu(NR2H)OPh (2) Calculated geometry Cu1 O2 O3 O4 O5 O6 N7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 Atom X 0 2.9797 -1.6469 1.0327 -1.0738 -3.7943 1.6627 3.2782 -3.2949 -2.8817 -2.3651 2.2456 -2.8298 1.7051 2.9291 -4.6807 1.8024 3.0232 4.553 -5.1549 2.5627 -1.9106 -4.2421 4.8519 3.8446 -3.3902 Y 0 -1.6726 0.3209 0.3297 -0.3635 0.439 -0.516 0.2916 -0.2089 -0.8628 -0.4657 0.8594 0.1929 -1.9803 -2.3784 -0.3458 0.2118 -0.2649 0.8402 -0.7283 1.9975 -1.1364 -0.9842 1.9615 2.5323 0.8329 Z 0 -3.3635 1.0741 1.57 -1.5356 1.6038 -1.0957 2.3319 -0.5924 -2.9149 -1.6423 1.5578 0.7187 -1.3179 -2.128 -0.8264 -2.3779 -3.1487 2.336 -2.0553 0.787 -4.0255 -3.0915 1.5638 0.7905 2.93 332 H27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37 H38 H39 H40 H41 H42 H43 H44 H45 H46 H47 H48 H49 2.4466 0.7942 1.7132 3.8432 2.8949 -5.3669 1.883 0.8942 3.0576 3.9409 5.3255 -6.218 1.7797 -1.3095 -2.4362 -1.2062 -4.6158 5.8491 4.0567 -2.8172 -2.7915 -4.3171 3.0509 -0.2577 -2.2594 -2.4799 -2.1792 -3.4407 -0.1463 1.2781 0.0386 0.2046 -0.0036 0.3835 -0.8336 2.4529 -0.2521 -1.4392 -1.9256 -1.2879 2.3823 3.4071 1.7579 0.0494 0.9786 -0.5845 -0.4982 -1.8478 -0.3483 -1.5512 -2.37 -0.0164 -2.1648 -2.9525 -4.1318 -2.6032 2.9442 -2.2263 0.1904 -4.2525 -4.9313 -3.7511 -4.0635 1.5669 0.1865 2.8925 3.3916 3.4765 2.9276 333 LCu(NR2H)(NR2)(3) Calculated geometry Cu1 O2 O3 O4 O5 N6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 H20 H21 H22 H23 H24 H25 H26 Atom X 0 4.2144 -1.3205 -1.6481 -3.1551 1.5956 -3.2338 -3.5574 -2.7606 -2.4684 1.9506 3.0763 -4.4631 2.7797 3.8726 -5.2194 -3.0613 -4.7567 -2.4631 2.2844 1.0677 2.737 3.4074 -4.8081 2.5059 3.1969 Y 0 0.2967 0.4941 -0.026 0.1815 0.7679 -0.5779 -1.2275 -0.5864 0.0726 1.1595 0.3311 -1.188 0.6108 -0.2271 -1.8023 -1.2473 -1.8132 0.7796 2.2085 1.1185 -0.6913 0.7748 -1.174 0.181 1.6104 Z 0 -1.4852 -1.8484 0.8824 -3.0776 -0.3768 -0.8575 1.4806 0.488 -1.9269 -1.7341 -2.3436 -1.1672 0.452 -0.2044 -0.1949 2.897 1.1257 -4.1856 -1.704 -2.3724 -2.5445 -3.2835 -2.1905 1.4168 0.6498 334 H27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37 C38 C39 C40 C41 C42 O43 H44 H45 H46 H47 H48 H49 H50 H51 4.7833 3.5475 -6.1594 -2.9481 -2.0762 -3.7513 -5.3482 -3.1718 -1.5748 -2.175 -0.8894 0.8931 0.9159 0.1788 0.7283 0.6868 1.4247 -0.1365 1.511 1.9573 0.4504 0.1454 1.7632 -0.3525 1.1493 -0.2071 -1.2695 -2.2744 -0.2347 -1.7156 -1.7945 -2.2997 0.7664 0.2016 1.803 -2.1848 -4.0354 -2.4939 -1.9779 -2.5297 -4.0662 -4.5225 -4.3946 -4.4512 -2.168 -2.1653 -2.2074 -2.231 -4.4139 -4.5166 0.3957 -0.3082 -0.4487 3.2923 2.963 3.5395 1.8937 -5.0089 -4.4385 -3.9482 0.0109 1.0918 1.1417 -0.0661 -1.3556 -1.2582 -0.1319 1.2199 1.8882 1.1449 2.0728 -2.2205 -1.5092 -1.1893 -2.137 335 LCu(NR2)R (4-R) Calculated geometry Cu1 O2 O3 O4 O5 N6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 H20 H21 H22 H23 Atom X 0 4.2144 -1.3205 -1.6481 -3.1551 1.5956 -3.2338 -3.5574 -2.7606 -2.4684 1.9506 3.0763 -4.4631 2.7797 3.8726 -5.2194 -3.0613 -4.7567 -2.4631 2.2844 1.0677 2.737 3.4074 Y 0 0.2967 0.4941 -0.026 0.1815 0.7679 -0.5779 -1.2275 -0.5864 0.0726 1.1595 0.3311 -1.188 0.6108 -0.2271 -1.8023 -1.2473 -1.8132 0.7796 2.2085 1.1185 -0.6913 0.7748 Z 0 -1.4852 -1.8484 0.8824 -3.0776 -0.3768 -0.8575 1.4806 0.488 -1.9269 -1.7341 -2.3436 -1.1672 0.452 -0.2044 -0.1949 2.897 1.1257 -4.1856 -1.704 -2.3724 -2.5445 -3.2835 336 H24 H25 H26 H27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37 C38 C39 C40 C41 C42 O43 H44 H45 H46 H47 H48 H49 H50 H51 -4.8081 2.5059 3.1969 4.7833 3.5475 -6.1594 -2.9481 -2.0762 -3.7513 -5.3482 -3.1718 -1.5748 -2.175 -0.8894 0.8931 0.9159 0.1788 0.7283 0.6868 1.4247 -0.1365 1.511 1.9573 0.4504 0.1454 1.7632 -0.3525 1.1493 -1.174 0.181 1.6104 -0.2071 -1.2695 -2.2744 -0.2347 -1.7156 -1.7945 -2.2997 0.7664 0.2016 1.803 -2.1848 -4.0354 -2.4939 -1.9779 -2.5297 -4.0662 -4.5225 -4.3946 -4.4512 -2.168 -2.1653 -2.2074 -2.231 -4.4139 -4.5166 -2.1905 1.4168 0.6498 0.3957 -0.3082 -0.4487 3.2923 2.963 3.5395 1.8937 -5.0089 -4.4385 -3.9482 0.0109 1.0918 1.1417 -0.0661 -1.3556 -1.2582 -0.1319 1.2199 1.8882 1.1449 2.0728 -2.2205 -1.5092 -1.1893 -2.137 337 LCu(NR2H)2(OPh)R (1-R) Calculated geometry Cu1 O2 O3 O4 O5 O6 O7 N8 N9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 Atom X 0 1.8922 -1.1678 1.0214 -1.4736 -2.8479 -2.9873 1.1317 -0.8597 3.2886 -3.1293 -3.5571 -2.6454 1.9425 -2.2997 0.4086 1.3415 -4.4445 1.7575 2.6299 4.2878 -5.2837 1.6793 -1.9488 Y 0 3.2707 1.6898 -1.1333 -0.672 3.1226 -2.082 0.9937 -0.8938 -0.5007 1.0615 -1.0123 -0.2129 -0.2166 1.9309 1.3704 2.1157 1.4794 2.1937 2.9213 0.4542 0.693 1.1184 -0.0905 Z 0 -2.8921 0.0893 3.4555 -1.4068 -0.0779 3.1179 -1.331 1.5839 3.7911 -1.1603 -2.4081 -1.6282 3.433 -0.3582 -2.573 -3.515 -1.4784 -0.7162 -1.7274 3.6908 -2.2217 3.0181 2.1881 338 C25 C26 C27 C28 C29 C30 C31 C32 H33 H34 H35 H36 H37 H38 H39 H40 H41 H42 H43 H44 H45 H46 H47 H48 H49 H50 H51 H52 H53 H54 H55 H56 H57 H58 H59 H60 H61 H62 H63 H64 H65 C66 C67 -1.3716 -3.0716 -1.9509 -4.8233 -2.4969 4.0083 2.6899 -2.0811 1.8815 -0.4304 0.0215 2.1525 0.7908 -4.7858 2.3482 0.9534 3.007 3.4867 5.3046 -6.2882 0.6626 -2.7489 -1.5639 -0.5625 -2.1302 -2.1863 -3.8474 -2.7745 -2.3923 -1.1584 -5.4888 -1.7152 -3.3367 4.7927 2.4451 -1.1472 -1.8662 -2.7071 -0.0976 3.5212 1.2045 3.7971 2.9023 -2.255 -2.3442 -2.886 -0.5566 -0.7831 1.7479 2.0648 4.0212 0.3709 2.0048 0.4659 1.4525 2.4577 2.4381 1.8851 2.8392 3.8485 2.2916 0.1879 1.0227 1.3902 0.0327 0.8908 -2.8863 -2.1882 -2.235 -2.853 -2.9882 -3.8533 -3.0322 -1.1813 -0.8522 -0.2134 2.49 3.0683 4.2863 3.5702 4.9006 -0.966 -1.506 -1.8388 -2.1291 -0.8742 1.3074 -2.8988 2.5674 -2.6809 3.4299 3.2451 2.9222 0.7412 -1.6139 -2.3002 -3.0359 -3.8482 -4.391 -1.116 0.1445 -0.3691 -1.2964 -2.0062 3.9599 -2.4522 2.759 1.4589 2.4565 0.9442 0.5284 -3.5313 -3.4718 -2.0667 2.3265 3.3115 -3.268 4.1956 3.8284 3.1687 2.5896 0.2472 1.7089 0.8629 2.325 4.1249 1.0683 0.3812 0.2454 339 C68 C69 C70 O71 H72 H73 H74 H75 H76 H77 H78 H79 1.4944 1.31 2.3183 3.6439 3.549 4.8448 3.2559 3.0482 0.3031 1.5243 2.0422 2.3007 -1.3821 -2.2956 -3.4587 -2.9784 -2.6661 -1.8319 -0.3441 -0.2434 -2.7073 -1.7912 -4.0577 -4.096 0.1284 -1.049 -0.8801 -0.7449 1.3036 0.4151 -0.6406 1.1186 -1.1101 -1.9941 -0.0034 -1.7641 340 LCu(NR2H)(OPh)R (2-R) Calculated geometry Cu1 O2 O3 O4 O5 O6 N7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 Atom X 0 1.7609 -1.3195 1.4523 -1.3058 -3.2911 1.1186 3.7214 -3.2612 -3.3892 -2.5967 2.588 -2.5187 1.6025 2.4611 -4.6642 0.4542 1.3463 4.936 -5.4108 2.7373 -2.6951 -4.76 5.0724 3.9615 Y 0 4.5747 1.0181 -0.758 0.5964 1.6179 1.8087 -1.3627 1.0092 0.5459 0.7097 -1.0051 1.2006 2.3093 3.552 1.1358 2.8937 4.1211 -1.6245 0.9784 -0.9307 0.2247 0.6862 -1.5435 -1.1969 Z 0 -0.225 -1.5864 -0.9044 1.211 -2.4323 0.2074 -1.0279 -0.1644 2.2374 1.0622 -0.2692 -1.4144 -1.0974 -0.929 -0.18 0.9554 1.0601 -0.4136 0.9639 1.1295 3.5288 2.1685 0.9721 1.7327 341 C26 H27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37 H38 H39 H40 H41 H42 H43 H44 H45 H46 H47 H48 H49 H50 C51 C52 C53 C54 C55 O56 H57 H58 H59 H60 H61 H62 H63 H64 -2.6376 1.9291 0.7276 2.1657 3.385 2.7301 -5.1539 0.1864 -0.4683 0.8075 2.2308 5.7895 -6.4881 1.8793 -2.001 -2.1001 -3.4193 -5.3442 6.0233 4.0419 -3.4184 -2.1977 -1.8602 3.6195 -1.9432 -1.1234 -0.3707 -0.9423 -0.8998 -1.6264 -1.0454 -2.1746 -0.6725 0.6885 -0.4881 -1.4011 0.1261 -2.6909 -1.5389 1.8077 1.5013 2.5361 1.5173 3.3001 3.9664 1.3596 2.5293 3.1436 4.9464 3.8914 -1.8952 1.0753 -0.6805 1.0189 -0.6875 0.0924 0.557 -1.7498 -1.1338 2.1358 0.8734 2.5663 -1.426 -1.4327 -4.048 -2.7064 -1.7645 -2.3213 -3.6825 -4.5622 -3.9142 -4.7937 -2.891 -2.3262 -1.6666 -2.4758 -3.5392 -4.1698 -3.6981 0.7429 -1.7073 -1.5879 -0.3887 -1.901 -1.116 1.9456 0.4302 1.5267 1.6719 -1.0246 0.9336 1.743 3.8155 3.4403 4.3328 3.0731 1.4458 2.8118 -4.3785 -4.0451 -3.6162 -2.1044 0.1476 0.7815 0.9026 -0.1186 -1.5126 -1.4897 -0.5386 1.0691 1.4366 0.7202 1.9191 -2.2271 -1.8424 -1.2619 -2.4611 342 Morpholine (NR2H) H N O Calculated geometry O1 N2 C3 C4 C5 C6 H7 H8 H9 H10 H11 H12 H13 H14 H15 Atom X 0 -0.2916 -0.0751 -0.5746 0.2127 -0.2933 -1.2875 -1.6709 -0.294 -0.0741 1.3062 0.1892 -1.3799 0.9994 -0.5707 Y 0 2.6568 1.4884 0.1947 2.4063 1.0915 2.853 0.2201 -0.6739 3.2365 2.3796 0.8656 1.1476 1.4007 1.652 Z 0 -1.0631 -1.9232 -1.292 0.2913 0.872 -1.0148 -1.2041 -1.8903 0.9408 0.2478 1.8244 1.0343 -2.1137 -2.8829 343 Phenol (PhOH) OH Calculated geometry O1 C2 C3 C4 C5 C6 C7 H8 H9 H10 H11 H12 H13 Atom X 0 2.2569 0.9514 3.2583 0.653 2.9711 1.6651 4.2712 -0.3651 3.7556 1.4267 2.4716 -0.8584 Y 0 0.6381 0.9763 1.5972 2.2696 2.8924 3.2207 1.3286 2.5259 3.6356 4.224 -0.3709 0.3536 Z 0 0.2604 -0.0905 0.1834 -0.5151 -0.2402 -0.588 0.4572 -0.7866 -0.2981 -0.9192 0.5887 -0.2669 344 Organic radical (R) O Calculated geometry C1 C2 O3 C4 C5 C6 H7 H8 H9 H10 H11 H12 H13 H14 H15 Atom X 0 -1.4941 -2.2835 -2.1418 -0.6982 0.2537 0.3155 0.5711 -1.7991 -1.7193 -2.8266 -2.4508 -0.497 -0.5949 1.1964 Y 0 -0.025 0.4326 -0.4031 -0.4083 -0.6758 1.0556 -0.4585 -1.0459 0.635 -0.0113 -1.426 0.5803 -1.1402 -1.173 Z 0 -0.3388 0.7557 1.9012 2.4151 1.3021 0.0495 -0.8114 -0.6061 -1.1769 2.6537 1.6462 2.8607 3.2203 1.4907 345 3: Copper-catalyzed asymmetric azidation of alkyl halides 3.1: Background (A) PPh2 O R1 R2 N N N R3 R1 Br alkyl O R1 cycloaddition R2 (B) 1 O NHAr phosphoramidite synthesis P(OR)3 R1 O R2 R3 HN Staudinger ligation N3 reduction [H] Cu/L* CsOPh•2H2O TMSN3 CO2R3 R2 O NH2 (alkyl )H R3 [Cu] R1 O O R2 HN OR P OR O O 1 (alkyl )H ° Toluene/DME, -78 C (blue LED) hν N3 alkyl O O NHAr O PAr12 PAr12 L* O = 3,5-(t-Bu) Ar1 2-4-(Meo)(C6H2) Figure 3.1.1: (A) Selected useful transformations of alkyl azides. (B) Enantioconvergent azidation of secondary and tertiary α-bromo amides. Azides are valuable motifs in synthetic organic chemistry and find wide use as a synthetic intermediate, for example as an intermediate in the Curtius rearrangement.63 In particular, chiral alkyl azides are interemediates in click chemistry reactions64 such as Huisgen cycloaddition,65 and Staudinger ligation.66–68 Other useful transformations include reduction to amines,69 tetrazole,70 and phosphoramide synthesis, and others (Fig. 3.1.1A). A variety of methods have been reported for the synthesis of enantioenriched alkyl azides including ring-opening approaches,71,72 azidofunctionalization of olefins,73–76 decarboxylation,77,78 and C-H functionalization.79–81 Conceptually, the most simple synthesis approach is the nucleophilic substitution by azide, however few asymmetric methods of this type have been reported.82–84 Given this literature 346 backdrop, our group sought to developed a general method for the asymmetric synthesis of α-azido carbonyl compounds from racemic α-halo carbonyl precursors. After optimization, we devised a catalytic protocol using a copper-photocatalyst to achieve the enantioconvergent synthesis of αazido amides from secondary and tertiary alkyl halides using TMSN3 as an azide source in the presence of the base cesium phenoxide. Using this protocol, a diverse range of secondary and tertiary azides could be synthesized. (Fig 3.1.1B). EPR and 31P-NMR spectroscopy indicates that the primary CuII species in solution was a DTBM-SEGPHOS-Cu-azide complex. However, it was ambiguous whether or not the CuII species was the neutral diazide species LCuII(N3)2 or the cationic species LCuII(N3)+. 3.2: EPR calculations of CuII-azide species To disambiguate the identity of the dominant CuII species in solution, a dual strategy of EPR measurements as well as DFT experiments was undertaken. The geometry of both putative CuII species were computed, and their EPR hyperfine couplings calculated. Figure 3.2.1 shows the results of both the reported and calculated EPR values. From the table, the measured 31P couplings of the two phosphorus atoms are close together, which matches closely with the computed values for LCuII(N3)2. In contrast, these values are divergent from each other in the case of LCu(N3)+. Further, the experimental couplings for 14N nuclei is closer in value to the calculated values for Figure 3.2.1: Comparison of experimental EPR parameters with calculated values for LCuII(N3)2 and LCuII(N3)+. 347 LCuII(N3)2. Based on this evidence and further analogy to the previously reported LCuIICl2, the structure of the dominant CuII species in solution was assigned to LCuII(N3)2.85 3.3: Computational details 3.3.1: Computational methods All calculations were performed using the Orca 6.0.1 software package.28,29,86 All molecular structure images were generated using the Mercury software package.27 Geometry optimizations were carried out using the B3LYP87 functional with the D4 dispersion correction. ` The Def2-SVP basis set was used for all atoms except copper, for which the Def2-QZVPPD basis set was used.35,36 The RIJCOSX approximation was used with the def2/J auxiliary basis set in all calculations.88,89 All calculations included the implicit CPCM solvation model.39 A dielectric constant of 7.20,90 a refractive index of 1.38,91 and a solvent radius of 2.42 Å were used to approximate 1,2-dimethoxyethane. EPR values for LCuII(N3)2 and [LCuII(N3)]+ were calculated using the TPSSh functional92,93 based on literature examples showing its effectiveness in modeling spin states of bioinorganic compounds.94 The Def2-TZVPD basis set was used for all atoms except copper, for which def2-QZVPPD was used. EPR values were calculated for all Cu, P, and N atoms. 348 3.3.3.2: Calculated structures LCuII(N3)2 Calculated geometry Cu1 P2 N3 P4 N5 C6 C7 H8 C9 C10 C11 H12 H13 H14 C15 H16 H17 H18 C19 H20 H21 H22 C23 Atom X 0 1.2806 -1.3068 1.8845 -1.3139 0.2627 -0.9604 -1.2603 -1.8099 -3.1133 -3.5114 -3.8181 -2.6749 -4.3542 -4.2593 -5.1848 -4.0121 -4.4707 -2.9257 -2.058 -2.8018 -3.8225 -1.3952 Y 0 1.3682 -1.4807 -1.1402 1.4299 2.1375 1.5526 0.6538 2.0813 1.3078 1.3985 2.401 1.0867 0.7143 1.8097 1.2513 1.6496 2.8776 -0.2004 -0.6128 -0.4169 -0.7448 3.2885 Z 0 1.3574 -0.0662 -0.7107 -0.4596 2.6558 2.9731 2.4395 3.9569 4.2755 5.7649 6.0781 6.4113 5.9524 3.3672 3.5866 2.3062 3.5059 3.9805 4.5186 2.9099 4.3136 4.5768 349 C24 H25 H26 H27 O28 C29 C30 C31 H32 H33 H34 C35 H36 H37 H38 C39 H40 H41 H42 C43 H44 C45 C46 H47 C48 C49 C50 H51 H52 H53 C54 H55 H56 H57 C58 H59 H60 H61 C62 O63 C64 H65 H66 -3.291 -3.1288 -3.3773 -4.2354 -2.1982 0.4327 -0.1112 0.4088 0.8141 1.0354 -0.6099 -0.3811 0.1115 -1.4005 -0.4378 1.8962 2.0004 2.5602 2.2597 0.6886 1.6614 2.0626 1.5875 0.8284 2.0476 1.534 2.3091 1.9873 3.3938 2.1217 0.0352 -0.3513 -0.1354 -0.5588 1.6933 1.1267 2.7508 1.328 2.9422 3.26 2.2653 1.3451 2.6892 4.7079 5.035 5.5942 4.145 3.9291 5.0626 3.8582 4.7386 5.5894 3.8576 4.5351 6.3435 7.2083 6.2903 6.54 5.3704 5.6775 4.5092 6.2018 3.2655 3.6903 2.7261 3.0092 2.3604 4.1082 4.2269 5.2201 5.0733 5.0433 6.2699 4.6001 4.6491 5.5798 3.8531 2.8442 2.0486 2.5413 2.9012 4.9835 6.1975 7.2048 6.9643 8.1378 5.0097 3.9708 5.6559 5.069 5.4871 5.1404 4.3388 6.6511 7.2236 6.8671 7.0033 4.8558 5.33 5.2517 3.7728 4.7627 3.7104 4.9354 5.3861 3.3596 3.1325 0.4361 -0.8403 -1.2706 -1.581 -3.0374 -3.9269 -4.9706 -3.8797 -3.676 -3.0275 -4.0589 -2.5547 -2.478 -3.7182 -3.2169 -3.743 -4.7556 -0.9246 -1.4841 -1.3252 -1.88 -1.722 350 H67 C68 C69 C70 H71 H72 C73 H74 H75 H76 C77 H78 H79 H80 C81 H82 C83 C84 H85 C86 H87 C88 O89 O90 C91 C92 C93 C94 O95 O96 C97 C98 H99 C100 H101 C102 C103 C104 H105 C106 C107 C108 H109 2.0065 3.5583 4.7328 5.8482 5.5126 6.1503 4.2893 3.4279 4.0218 5.1156 5.3308 6.2041 5.6621 4.6133 3.0952 3.5349 3.3788 3.7664 3.1842 4.8966 5.1921 5.6242 6.7524 6.1184 5.239 4.1128 3.8034 4.746 5.9572 5.6431 4.5516 3.3881 3.2252 2.4313 1.5165 2.6204 1.4363 0.4245 0.0421 -0.1452 -1.2623 -2.609 -2.5572 7.3456 4.6451 5.4618 5.5822 6.1706 4.5897 6.8713 6.815 7.5134 7.363 4.7626 5.3356 3.7391 4.7183 3.5041 3.2116 -0.139 0.1656 -0.2294 0.9541 1.185 1.4017 2.1691 1.6885 1.1069 0.3653 0.0952 -0.5813 -1.0556 -1.6148 -0.927 -0.5967 -0.871 0.132 0.4379 0.489 -1.9385 -1.3447 -0.3756 -1.9714 -1.2074 -1.4372 -1.0715 -0.2633 0.3142 0.8985 -0.165 -1.028 -0.5304 1.3473 2.0322 0.5007 1.8867 2.1356 2.484 1.9109 2.9699 0.9731 1.9239 -0.9964 -2.3065 -3.14 -2.5888 -3.6131 -1.5034 -1.4734 0.6725 -0.1934 0.1174 1.5424 2.2988 1.8869 4.0831 3.6376 4.305 5.3481 3.5763 4.0849 2.2343 -2.2784 -3.0284 -2.7133 -4.1438 -4.8936 -4.1693 -3.1312 351 H110 H111 C112 H113 H114 H115 C116 H117 H118 H119 C120 O121 C122 H123 H124 H125 C126 C127 C128 H129 H130 H131 C132 H133 H134 H135 C136 H137 H138 H139 C140 H141 C142 C143 H144 C145 C146 C147 H148 H149 C150 H151 H152 -2.888 -3.4158 -0.9705 -1.7176 0.0273 -1.034 -1.3713 -1.7389 -0.394 -2.0694 0.3247 -0.2868 -1.5024 -1.5456 -1.5387 -2.379 1.453 2.109 2.4942 2.9763 3.2102 1.614 1.1724 1.7246 0.3086 0.8055 3.4028 3.2078 4.1312 3.8757 1.9737 2.7902 2.3603 3.5793 4.3065 3.8741 5.2412 6.203 6.3475 5.8504 5.0692 4.5959 4.4609 -2.499 -0.8887 0.3132 0.8366 0.5397 0.7425 -1.5852 -2.6014 -1.4919 -0.8901 -3.2733 -4.0331 -4.6863 -4.877 -5.6444 -4.0886 -3.8427 -5.1625 -5.0556 -5.9904 -4.2323 -4.8764 -6.3701 -7.3059 -6.36 -6.396 -5.4465 -5.6208 -4.6251 -6.3564 -3.1586 -3.5938 -2.4583 -3.1339 -2.809 -4.2093 -4.9217 -4.1281 -3.0976 -4.0872 -6.3175 -6.2361 -6.9897 -4.135 -4.6832 -4.8627 -5.479 -5.2701 -3.853 -6.386 -6.5574 -6.8863 -6.8792 -4.4484 -5.4145 -5.0521 -3.9685 -5.5908 -5.3474 -3.7926 -4.2556 -5.748 -6.0791 -5.9054 -6.3781 -4.0323 -4.2195 -4.7053 -2.9936 -3.4662 -2.3967 -3.553 -3.8669 -2.6919 -2.1229 0.4431 0.3554 -0.3851 1.1991 1.082 0.1732 0.5288 -0.869 0.4446 -0.5468 1.0597 352 H153 C154 H155 H156 C157 O158 C159 H160 H161 H162 C163 C164 C165 H166 H167 H168 C169 H170 H171 H172 C173 H174 H175 H176 C177 H178 H179 C180 C181 H182 H183 H184 H185 H186 H187 N188 N189 N190 N191 6.0558 5.917 5.3943 5.9259 2.8827 3.1556 2.536 2.0894 1.7562 3.3052 1.6932 0.6399 -0.376 -1.1671 0.0859 -0.8521 1.2823 2.0179 1.7951 0.5001 -0.164 -0.8079 0.4955 -0.8254 1.4576 0.5453 6.7338 7.2346 6.6475 7.2231 7.2957 6.9598 7.6135 8.0137 7.1832 -1.1919 -1.1212 -2.4889 -3.6281 -6.7914 -5.0495 -5.7638 -4.0805 -4.5983 -5.6907 -6.9391 -6.9472 -7.1658 -7.7247 -3.8506 -4.1063 -5.1663 -5.3038 -6.1439 -4.8392 -4.5222 -3.7676 -5.488 -4.5839 -2.8165 -2.516 -1.9706 -2.9946 -2.7994 -2.2179 6.0741 2.0723 -1.4012 -2.3221 -0.5589 -5.3842 3.0471 1.2891 -4.6294 -2.606 -3.702 1.206 1.019 0.3102 2.4669 3.1123 2.9876 2.1452 2.9287 2.6403 1.6341 3.3849 2.6981 2.3383 3.4426 2.9586 3.7146 2.7753 2.0206 4.7832 5.1075 4.739 5.5567 3.7339 2.8951 3.9801 4.5953 1.4451 1.5368 0.2699 -0.1301 3.0874 2.9328 3.394 2.3439 0.2021 -0.0747 0.1647 -0.4597 -0.8259 -0.3713 -0.2971 353 LCuII(N3)+ Calculated geometry Cu1 P2 N3 P4 C5 C6 H7 C8 C9 C10 H11 H12 H13 C14 H15 H16 H17 C18 H19 H20 Atom X 0 1.2021 -1.5084 1.8309 0.1891 -0.9717 -1.235 -1.8032 -3.0219 -3.4037 -3.8239 -2.528 -4.1582 -4.2253 -5.091 -3.9777 -4.5319 -2.6925 -1.7798 -2.5628 Y 0 1.4248 -0.9095 -1.1174 2.1726 1.5189 0.5738 2.0352 1.1845 1.3841 2.3701 1.2388 0.6308 1.4889 0.8708 1.2559 2.5424 -0.3206 -0.5894 -0.6321 Z 0 1.2758 -0.6313 -0.8497 2.5892 2.9984 2.5255 4.0048 4.4405 5.9236 6.1424 6.5762 6.2002 3.5199 3.8102 2.4717 3.5646 4.2923 4.8464 3.2462 354 H21 C22 C23 H24 H25 H26 O27 C28 C29 C30 H31 H32 H33 C34 H35 H36 H37 C38 H39 H40 H41 C42 H43 C44 C45 H46 C47 C48 C49 H50 H51 H52 C53 H54 H55 H56 C57 H58 H59 H60 C61 O62 C63 -3.5252 -1.4496 -3.4157 -3.2659 -3.5872 -4.3076 -2.2628 0.2809 -0.2185 0.3479 0.7222 1.04 -0.6383 -0.6281 -0.1632 -1.6166 -0.7603 1.7014 1.7344 2.4275 2.0402 0.5724 1.5012 1.9382 1.4193 0.6705 1.8395 1.3182 2.0117 1.6917 3.1063 1.7459 -0.2031 -0.5879 -0.4423 -0.7485 1.5894 1.1088 2.6697 1.2035 2.7275 2.9932 1.9687 -0.9139 3.3012 4.6154 4.9504 5.4928 3.9719 3.9411 5.2089 3.941 4.9394 5.8352 4.109 4.6858 6.4241 7.3362 6.327 6.5703 5.593 5.8655 4.7826 6.4686 3.3577 3.8361 2.7879 3.0843 2.4184 4.2069 4.3317 5.4024 5.2572 5.307 6.4283 4.5954 4.6504 5.5457 3.7921 2.9826 2.1309 2.7781 3.0219 5.0907 6.3235 7.2936 4.6995 4.5376 4.9363 3.898 5.5766 4.9843 5.4354 4.942 4.2135 6.4623 6.9847 6.678 6.8706 4.6555 5.0638 5.1164 3.5712 4.481 3.4149 4.6504 5.0553 3.2222 2.9278 0.3356 -0.9214 -1.3527 -1.6522 -3.1051 -3.9715 -5.0158 -3.9369 -3.6931 -3.0917 -4.1231 -2.589 -2.5715 -3.8151 -3.3165 -3.8603 -4.8454 -0.9971 -1.5351 -1.3286 355 H64 H65 H66 C67 C68 C69 H70 H71 C72 H73 H74 H75 C76 H77 H78 H79 C80 H81 C82 C83 H84 C85 H86 C87 O88 O89 C90 C91 C92 C93 O94 O95 C96 C97 H98 C99 H100 C101 C102 C103 H104 C105 C106 1.0265 2.3286 1.7731 3.3888 4.5645 5.6479 5.2804 5.9544 4.1158 3.2678 3.8289 4.9477 5.2019 6.0739 5.5444 4.5039 2.971 3.4406 3.2757 3.6351 3.0516 4.7447 5.0226 5.4801 6.5932 6.0004 5.1195 4.0132 3.7343 4.7023 5.9113 5.6481 4.539 3.384 3.2474 2.4016 1.4936 2.5608 1.3417 0.5006 0.2427 -0.0484 -0.9541 7.0048 8.2352 7.4412 4.7401 5.5691 5.711 6.3001 4.7253 6.9706 6.902 7.6173 7.4637 4.8682 5.4514 3.852 4.8054 3.5749 3.274 -0.0673 0.2528 -0.1513 1.0629 1.3027 1.5178 2.2981 1.8025 1.211 0.4476 0.1665 -0.4944 -0.9473 -1.507 -0.841 -0.5302 -0.8056 0.1838 0.4774 0.541 -1.9439 -1.2803 -0.2418 -1.9239 -1.0921 -1.8198 -1.7654 -0.2542 0.2143 0.777 -0.3166 -1.1663 -0.6963 1.246 1.9458 0.4094 1.7747 1.9928 2.3264 1.7518 2.8426 0.8598 1.7936 -1.1433 -2.4597 -3.2876 -2.7536 -3.7805 -1.6755 -1.6609 0.4938 -0.359 -0.034 1.3958 2.1335 1.6994 3.9031 3.4776 4.1681 5.2146 3.459 3.9866 2.1143 -2.3843 -3.2772 -3.0779 -4.3937 -5.3335 356 C107 H108 H109 H110 C111 H112 H113 H114 C115 H116 H117 H118 C119 O120 C121 H122 H123 H124 C125 C126 C127 H128 H129 H130 C131 H132 H133 H134 C135 H136 H137 H138 C139 H140 C141 C142 H143 C144 C145 C146 H147 H148 C149 -2.4057 -2.4499 -2.8173 -3.06 -0.4949 -1.0765 0.5717 -0.6576 -0.8948 -1.3429 0.1478 -1.4346 0.2452 -0.3545 -1.6945 -1.9381 -1.7834 -2.4136 1.194 1.6773 2.2539 2.6115 3.11 1.4992 0.5358 0.948 -0.2224 0.0409 2.8006 2.4527 3.6632 3.158 1.7079 2.3897 2.2926 3.5291 4.2793 3.7957 5.1777 6.1485 6.267 5.8205 5.0693 -1.1189 -0.6887 -2.1348 -0.5187 0.3847 0.9407 0.4759 0.8876 -1.5573 -2.5402 -1.5972 -0.8289 -3.3052 -4.0465 -4.4901 -4.527 -5.4999 -3.8336 -3.9717 -5.4135 -5.5041 -6.5284 -4.8194 -5.2498 -6.4379 -7.4595 -6.3634 -6.3086 -5.8177 -5.8532 -5.1351 -6.8253 -3.2685 -3.7627 -2.4161 -3.0646 -2.6973 -4.1841 -4.8709 -4.0682 -3.0316 -4.0453 -6.2827 -4.8018 -3.7883 -4.7504 -5.4557 -5.3407 -6.0918 -5.5996 -4.3779 -6.8047 -6.976 -7.159 -7.4303 -4.5469 -5.5302 -5.3176 -4.2449 -5.7439 -5.8314 -3.723 -3.9955 -5.426 -5.6217 -5.5429 -6.1807 -3.8144 -3.8516 -4.6008 -2.8383 -3.019 -1.9749 -3.0701 -3.2806 -2.6318 -1.947 0.3188 0.2531 -0.4433 1.0451 0.9715 0.0823 0.4282 -0.9689 0.3551 357 H150 H151 H152 C153 H154 H155 C156 O157 C158 H159 H160 H161 C162 C163 C164 H165 H166 H167 C168 H169 H170 H171 C172 H173 H174 H175 C176 H177 H178 C179 C180 H181 H182 H183 H184 H185 H186 N187 N188 4.5768 4.5151 6.0793 5.7954 5.2184 5.8218 2.7644 2.9953 2.3192 2.0708 1.397 2.9947 1.5693 0.4938 -0.6225 -1.4131 -0.249 -1.0807 1.0702 1.9109 1.424 0.285 -0.158 -0.755 0.5969 -0.8442 1.3504 0.4171 6.5378 7.0955 6.6304 7.1992 7.2871 6.8283 7.4438 7.9008 7.1375 -1.6552 -1.8355 -6.2436 -6.9795 -6.6999 -4.9558 -5.6231 -3.9639 -4.6377 -5.8004 -6.9787 -6.9261 -7.1456 -7.8292 -3.9021 -4.1903 -5.07 -5.2494 -6.0458 -4.5682 -4.8349 -4.2401 -5.8602 -4.8574 -2.8615 -2.3829 -2.138 -3.0641 -2.8174 -2.2636 6.2135 2.222 -1.2951 -2.2179 -0.4548 -5.3349 3.2104 1.4664 -4.5511 -2.0466 -3.1262 -0.6293 0.9927 0.2104 2.3859 3.037 2.861 1.9182 2.6036 2.1697 1.0981 2.7475 2.342 2.1178 3.192 2.5852 3.3325 2.2469 1.7176 4.4707 4.8627 4.327 5.2429 3.6474 2.8587 3.9921 4.4832 1.2598 1.3348 0.0964 -0.3217 2.8843 2.7158 3.1755 2.3223 0.0031 -0.2749 0.1056 -0.9934 -1.3505 358 4. 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