Kinetic Studies of Hydrogen Oxidation by Cobaloximes and Synthesis, Spectroscopy and Boronation of a New Heteroleptic Ruthenium Cyanide Complex Citation Del Ciello, Sarah Anne (2020) Kinetic Studies of Hydrogen Oxidation by Cobaloximes and Synthesis, Spectroscopy and Boronation of a New Heteroleptic Ruthenium Cyanide Complex. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/6QTC-G360. https://resolver.caltech.edu/CaltechTHESIS:11152019-095230239 Abstract Cobaloximes are macrocyclic complexes well-studied as homogeneous catalysts for hydrogen evolution, but they are also competent at the microscopic reverse reaction, hydrogen oxidation. Kinetic studies of Co(dmgBF 2 ) 2 L 2 reacting with hydrogen and base reveal a rate law that is second-order in cobalt and first-order in H 2 , indicating that the mechanism of H-H bond breaking is homolytic. The reduction potentials of metal cyanide complexes can be tuned by appending boranes to the N-terminus. By boronating ruthenium cyanide complexes containing diimine ligands, the Ru II/III couple can be tuned without drastic modification of the diimine 0/- couple. A new member of the [Ru(dimmine)(CN)4] 2- family is synthesized with the ligand 4,4’-bis(trifluoromethyl)-2,2’-bipyridine ( CF3 bpy) and boronated, resulting in a molecule with two reversible redox events separated by 3.2 V. Item Type: Thesis (Dissertation (Ph.D.)) Subject Keywords: hydrogen, cobaloximes, boranes, cobalt, ruthenium, cyanide, bipyridine Degree Grantor: California Institute of Technology Division: Chemistry and Chemical Engineering Major Option: Chemistry Thesis Availability: Public (worldwide access) Research Advisor(s): Gray, Harry B. Thesis Committee: Reisman, Sarah E. (chair) Gray, Harry B. Peters, Jonas C. See, Kimberly Defense Date: 22 November 2019 Funders: Funding Agency Grant Number National Science Foundation (NSF) CHE-1305124 National Science Foundation (NSF) CHE-1763429 Record Number: CaltechTHESIS:11152019-095230239 Persistent URL: https://resolver.caltech.edu/CaltechTHESIS:11152019-095230239 DOI: 10.7907/6QTC-G360 ORCID: Author ORCID Del Ciello, Sarah Anne 0000-0002-7571-8944 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 13577 Collection: CaltechTHESIS Deposited By: Sarah Del Ciello Deposited On: 20 Dec 2019 17:59 Last Modified: 26 May 2021 04:21 Thesis Files Preview PDF (Full thesis PDF) - Final Version See Usage Policy. 2MB Preview PDF (Chapter 1) - Final Version See Usage Policy. 632kB Preview PDF (Chapter 2) - Final Version See Usage Policy. 1MB Preview PDF (Chapter 3) - Final Version See Usage Policy. 1MB Repository Staff Only: item control page

Kinetic Studies of Hydrogen Oxidation by Cobaloximes and Synthesis, Spectroscopy and Boronation of a New Heteroleptic Ruthenium Cyanide Complex Thesis by Sarah Anne Del Ciello In Partial Fulfillment of the Requirements for the degree of Doctor of Philosophy Division of Chemistry and Chemical Engineering CALIFORNIA INSTITUTE OF TECHNOLOGY Pasadena, California 2020 (Defended November 22, 2019) ii Dedicated to Emmy the cat and Opal the cat, and Dan and Jess and Wojtus and all my friends and family; without your support, this thesis would not exist.  2020 Sarah Anne Del Ciello ORCID: 0000-0002-7571-8944 iii ACKNOWLEDGEMENTS My path to this degree and this thesis has wound through many valleys and over a few peaks; it is easily the most difficult thing I have accomplished to date. I could not have made it to this point alone, and I am humbled and grateful for those who helped me get here. Thanks are first and foremost owed to my husband, Dan, who after four years of loving and supporting me from down the dorm room hall, took a leap of faith with me and endeavored to make PhDs, long-distance dating, and later marriage work all at the same time. Without his support, cheerleading, and occasional supplying of cake and beer to soothe my bruised ego, I might have quit years ago. I’d also like to thank Dr. Steve Baldwin and the late great Prof. Greg Hillhouse, whose mentorship during my undergraduate research led me to the decision that not only did I want a PhD, but a Caltech PhD. Steve taught me most of the lab skills I still use today, and working in the Hillhouse lab ensured that I fell in love with all things colorful and terribly air-sensitive. If there is a Heaven, and I know Greg believed there was, I’m sure he’s there reading this thesis and thinking up some interesting reaction I should have done with one of his favorite small molecules. I consider myself incredibly fortunate to have been among the final few students to work with Prof. Harry Gray. Harry took me into his group at a time when rumors had it he was done taking students, and I was in a tough position, and for that I’m continually thankful. He has few peers when it comes to kindness toward students and enthusiasm for their work, and I was often relieved to work under someone who was unfazed that I’d rather be in Santa Barbara visiting my fiancé than in the lab on weekends. iv Thanks also to those members of the Gray and Peters groups who directly helped me learn the skills I needed throughout my time at Caltech: Wes and Aaron Sattler, who taught me how to use my Schlenk line (and actually appreciated my no-strikeout summer of softball); David Lacy and Nik Thompson, who taught me to use the hi-vac line; Bryan Hunter, who taught me that in situ spectroscopy only looks easy when he’s at the helm; Wes Kramer, whose work on group VI polypyridyl complexes laid the groundwork for my certainty that CF3 bpy will not coordinate to those metals; Jay Winkler and Javier Fajardo for their help with the laser spectroscopy; and especially Danh Ngo and Brendon McNicholas, who rescued me from the death of that group VI project with their considerable expertise synthesizing and boronating metal cyanides. My work with Danh and Brendon was the difference between this thesis being worth a Master’s and a doctorate, and so they have my eternal gratitude. I lived for five-ish years with Jess Sampson, and am grateful to her for being so incredibly accepting of our “third roommate” during the long-distance relationship period, for supplying our household with such a thorough complement of cookware, and for adopting such a sweet and loving cat in Opal, who hung out with me during countless emotional breakdowns. Speaking of cats, I’d be remiss to forget to thank Emmy, who will count this thesis as the fifth she has helped her human companions write. She was adopted as a stray by Dan and his three grad school roommates, all theoretical physicists, who named her for Emmy Noether. Despite her advanced age at adoption, she has been with us for three years and is a constant comfort. Finally, I should thank my family, without whom I would (literally) not be here, and my nongrad school friends, who have been such a relief to talk to when my world was consumed with frustrating science. Mom, Rachel, John, Wojtus, and all of my supportive in-laws have my gratitude for their love and support. v ABSTRACT Cobaloximes are macrocyclic complexes well-studied as homogeneous catalysts for hydrogen evolution, but they are also competent at the microscopic reverse reaction, hydrogen oxidation. Kinetic studies of Co(dmgBF2)2L2 reacting with hydrogen and base reveal a rate law that is second-order in cobalt and first-order in H2, indicating that the mechanism of H-H bond breaking is homolytic. The reduction potentials of metal cyanide complexes can be tuned by appending boranes to the N-terminus. By boronating ruthenium cyanide complexes containing diimine ligands, the RuII/III couple can be tuned without drastic modification of the diimine0/- couple. A new member of the [Ru(dimmine)(CN)4]2- family is synthesized with the ligand 4,4’bis(trifluoromethyl)-2,2’-bipyridine (CF3bpy) and boronated, resulting in a molecule with two reversible redox events separated by 3.2 V. vi PUBLISHED CONTENT AND CONTRIBUTIONS Ngo, Danh; Del Ciello, Sarah A., et al. “Cyano-Ambivalence: Spectroscopy and Photophysics of [Ru(diimine)(CN-BR3)4]2- Complexes.” Polyhedron, submitted. All authors participated in the conception and writing of the paper. S.A.D. synthesized the CF3 bpy-containing molecules and took the UV-Vis spectroscopic data and participated in the collection of the luminescence data of those molecules. S.A.D. also created all plots of the aforementioned data. Del Ciello, Sarah. A. et al. “Synthesis, Spectroscopy, and Boronation of a Fluorinated [Ru(bpy)(CN)4]2- Derivative” Manuscript in preparation for submission to Inorganic Chemistry. All authors participated in the conception and writing of the paper. S.A.D. synthesized the CF3 bpy-containing molecules, grew the crystals, took the NMR data, and participated in the collection of the electrochemical and IR data of those molecules. S.A.D. also created all plots of the aforementioned data except those of the electrochemistry. vii viii TABLE OF CONTENTS Acknowledgements………………………………………………………….......................iii Abstract …………………………………………………………………………………….v Published Content and Contributions…………………………………….............................vi Table of Contents……………………………………………………………. …………...vii Nomenclature…………………………………………………………………………….viii Chapter 1: Introduction: Renewable Energy Storage 1 Motivation: The Need for Storage 1 Hydrogen Evolution, Oxidation, and Fuel Cells 3 Redox Flow Batteries 5 Summary of this Dissertation 6 References 6 Chapter 2: Kinetic Studies of Hydrogen Oxidation by Cobaloximes 10 Introduction 10 Results 18 Discussion 24 Conclusion 26 References 26 Methods 33 Supporting Data 34 Chapter 3: Synthesis, Spectroscopy, and Boronation of a New Heteroleptic Ruthenium Cyanide Complex 43 Introduction 43 Results & Discussion 46 Conclusion 57 References 58 Methods 64 ix Supporting Data Appendix: Crystal Data 68 79 x NOMENCLATURE 2-MeTHF. 2-methyltetrahydrofuran. BCF. Tris(pentafluorophenyl)borane. bpy. 2,2’-bipyridine. Bu. N-butyl. CF3 bpy. 4,4’-bis(trifluoromethyl)-2,2’-bipyridine. DCM. Dichloromethane. DMF. Dimethylformamide. dmg. Dianion of dimethylgyloxime. dpg. Dianion of diphenylglyoxime. Et2O. Diethyl ether. HER. The hydrogen evolution reaction, 2H+ + 2e- → H2. HOR. The hydrogen oxidation reaction, H2 → 2H+ + 2e-. IR. Infrared. LMCT. Ligand-to-metal charge transfer. MeCN. Acetonitrile. MeOH. Methanol. MLCT. Metal-to-ligand charge transfer. NMR. Nuclear magnetic resonance. PEM. Proton-exchange membrane, a type of hydrogen fuel cell. Ph. Phenyl. xi phen. Phenanthroline. ppm. Parts per million. PPN. Bis(triphenylphosphine)iminium. py. Pyridine. SCE. Saturated calomel electrode, a reference electrode. THF. Tetrahydrofuran. TEMPO. (2,2,6,6,-Tetramethlpiperidin-1-yl)oxyl. TFA. Trifluoroacetic acid. 1 CHAPTER 1 INTRODUCTION: RENEWABLE ENERGY STORAGE Motivation: The Need for Storage Progress in generation of carbon-neutral renewable energy has been rapid over the last decade and is projected to grow to meet nearly half of world electricity demand by 2050 (Figure 1).1 As renewable energy becomes widespread and cost-competitive with fossil fuels, there will be increasing need for efficient, carbon-neutral storage technologies that can operate on a wide variety of time and power scales. 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% renewables natural gas Coal nuclear liquids 2010 2020 2030 2040 2050 Figure 1: Share of net electricity generation, world. Source: US. Energy Information Administration International Energy Outlook, September 2019 (Public Domain). 2 The most abundant sources of renewable energy, sunlight and wind, are intermittent and need to be stored at peak production to be used most efficiently. In California, where solar photovoltaics have become ubiquitous, the high production of solar energy has created a problem known as the “duck curve” (Figure 2).2 The peak of solar production occurs earlier in the day than peak electricity demand, resulting in a sharp rise in the net load on the grid as the sun sets, which requires generators to ramp up production very quickly. As solar gains even higher adoption rates, there will be an increasing number of sunny summer days where peak solar production outstrips demand and will need to be curtailed by grid operators, wasting energy. Wind power also varies on hourly, daily, and seasonal timescales that are uncoupled from demand, creating similar but even less predictable grid balancing and overgeneration problems.3 The grid-level ability to store energy from these intermittent sources during periods of high production to be used during periods of low production and high demand is key to reducing strain on power plants and electrical grids, lowering the cost of renewable energy, and increasing the penetration of renewables. Figure 2: Illustration of the “duck curve”. Created by Arnold Reinhold and reproduced under the Creative Commons Attribution-ShareAlike 4.0 International license. 3 A further challenge in the storage of renewable energy is applications such as long-range transportation and aviation which require energy sources that have a high energy density and fast refueling. These are the applications which are most difficult to transition from fossil fuels, which have high mass and volume energy densities (Figure 3).4 While there are increasing adoption rates for light duty electric vehicles, especially in large, newlyindustrialized countries such as China and India, the Li-ion batteries in those vehicles are too large and costly for heavy-duty applications such as freight transportation.5 Figure 3: Energy density comparison of transportation fuels. Source: Energy Information Administration (Public Domain). A wide variety of storage solutions will undoubtedly be needed for different sectors and different applications. Among the most efficient and flexible storage methods is electrochemical energy storage, wherein chemical oxidations and reductions store the energy – in short, batteries.6 The work in this dissertation represents fundamental science with potential applicability to two types of electrochemical energy storage technologies: hydrogen fuel cells and redox flow batteries. Hydrogen Evolution, Oxidation, and Fuel Cells Hydrogen derived from water splitting has been recognized as a key target for energy storage and fuel applications since the oil embargo of the 1970s.7,8 While the initial interest was in 4 developing alternatives to petroleum in order to secure energy independence from Middle Eastern oil producers, the climate crisis has renewed interest in hydrogen as a carbon-neutral energy source. Additionally, industrial feedstocks of hydrogen are currently primarily derived from steam reformation of hydrocarbons and the water-gas shift reaction, which are not only carbon intensive in their energy demands, but also produce CO2 as a coproduct.9 Development of renewable energy-fueled processes for producing hydrogen from water is therefore expected to be a key step toward the decarbonization of the global economy. Electro- or photoelectrocatalysts for the hydrogen evolution reaction (HER) are frequently targeted for use in the cathode of water electrolyzers, and there has been rapid progress in the development of Earth-abundant catalysts.10,11 However, a reversible catalyst which is also competent for the hydrogen oxidation reaction (HOR) has the advantage of being useful for water-based fuel cells, which are safer and more efficient than combustion at liberating energy from hydrogen. Hydrogen fuel cell cars additionally have several advantages over battery-powered electric vehicles, as they have longer driving ranges, faster refueling times, and are less disruptive to the electric grid.5 State-of-the-art commercial electolyzers and fuel cells both currently use Pt or IrO2 catalysts,12,13 which are too rare and expensive to be a scalable and economical solution long-term and are a major contributor to the higher cost of hydrogen cars.5 Thus, it is a critical area of research to identify Earth-abundant catalysts that are competent for HER and HOR to replace them. Naturally occurring hydrogenases are a typical source of inspiration in this field, since they are reversible and contain only Earth-abundant Fe and Ni.14 Indeed, a NiFe hydrogenase has been shown to catalyze HOR at a rate comparable to Pt.15 HOR catalyst development has occurred primarily in the solid-state material realm, but despite success in reducing the Pt loading for proton-exchange membrane (PEM) fuel cells,13 precious-metal-free catalysts are still unusual.16 Even less well-studied are Earth-abundant small-molecule catalysts which are capable of reversibly catalyzing the interconversion of protons and electrons with hydrogen. 5 Redox Flow Batteries Figure 4: Diagram of a vanadium-based redox flow battery. Reproduced with permission from the copyright holder, Elsevier, from reference 6. A redox flow battery (Figure 4) uses a solution-phase redox couple to store energy, as opposed to the solution-to-solid phase couples used by most conventional batteries. As the battery is charged, the charged electrolyte is pumped into a storage tank, and pumped back to the electrodes during discharge. Although it results in a low energy density, this design is advantageous for large, stationary applications such as grid balancing, since the capacity of the flow battery is as large as the storage tanks.6,17 Additionally, unlike hydrogen fuel cells, redox flow batteries have no need for catalysts to assist the charge and discharge process, as the transfer electrons directly with the electrode. A current limitation in redox flow battery technology is the reliance on water as the solvent. Water has an electrochemical stability window of only 1.23 V, limiting the cell voltage, and a high freezing point relative to outdoor temperatures during winter in much of the world. Non-aqueous redox flow battery electrolytes are desirable for applications where higher 6 voltages or lower working temperatures are needed, as there are many organic solvents which can overcome these limitations.18 In order to be a good candidate electrolyte for nonaqueous redox flow batteries, a molecule must have several properties. First, it must have a reversible electrochemical couple in the stability window of the desired solvent. Second, it must be stable in both the charged and discharged states over a long period of time and many charge/discharge cycles. Third, it should have high solubility in the solvent, which will improve the energy density of the battery. The difference in voltage between the reduction potentials of the two couples employed sets the maximum cell voltage. If the same molecule has two suitable couples, it can be used to make a symmetric redox flow battery, which confers additional stability to the system in the event of membrane crossover over time.19 Summary of this Dissertation Chapter Two of this dissertation focuses on one member of a series of macrocyclic Co catalysts that have been extensively studied for HER and its reaction with hydrogen. Further mechanistic information in this field is expected to aid the development of Earth-abundant catalysts for HER and HOR. Chapter Three of this dissertation describes the synthesis and boronation of a new Ru bipyridine cyanide complex. This work aimed to improve on previous work toward developing symmetric nonaqueous redox flow battery electrolytes using similar molecules. References (1) EIA projects that renewables will provide nearly half of world electricity by 2050 - Today in Energy - U.S. Energy Information Administration https://www.eia.gov/todayinenergy/detail.php?id=41533 (accessed Nov 6, 2019). (EIA) 7 (2) Confronting the Duck Curve: How to Address Over-Generation of Solar Energy https://www.energy.gov/eere/articles/confronting-duck-curve-how-address-overgeneration-solar-energy (accessed Nov 15, 2019). (3) Holttinen, H.; Meibom, P.; Orths, A.; Lange, B.; O’Malley, M.; Tande, J. O.; Estanqueiro, A.; Gomez, E.; Söder, L.; Strbac, G.; et al. Impacts of Large Amounts of Wind Power on Design and Operation of Power Systems, Results of IEA Collaboration. Wind Energy 2011, 14 (2), 179–192. https://doi.org/10.1002/we.410. (4) Few transportation fuels surpass the energy densities of gasoline and diesel - Today in Energy - U.S. Energy Information Administration (EIA) https://www.eia.gov/todayinenergy/detail.php?id=9991 (accessed Nov 15, 2019). (5) Cano, Z. P.; Banham, D.; Ye, S.; Hintennach, A.; Lu, J.; Fowler, M.; Chen, Z. Batteries and Fuel Cells for Emerging Electric Vehicle Markets. Nat. Energy 2018, 3 (4), 279–289. https://doi.org/10.1038/s41560-018-0108-1. (6) Alotto, P.; Guarnieri, M.; Moro, F. Redox Flow Batteries for the Storage of Renewable Energy: A Review. Renew. Sustain. Energy Rev. 2014, 29, 325–335. https://doi.org/10.1016/j.rser.2013.08.001. (7) Gray, H. B. Powering the Planet with Solar Fuel. Nat Chem 2009, 1 (1), 7–7. https://doi.org/10.1038/nchem.141. (8) Holladay, J. D.; Hu, J.; King, D. L.; Wang, Y. An Overview of Hydrogen Production Technologies. Catal. Today 2009, 139 (4), 244–260. https://doi.org/10.1016/j.cattod.2008.08.039. (9) Shaner, M. R.; Atwater, H. A.; Lewis, N. S.; McFarland, E. W. A Comparative Technoeconomic Analysis of Renewable Hydrogen Production Using Solar Energy. Energy Environ. Sci. 2016, 9 (7), 2354–2371. https://doi.org/10.1039/C5EE02573G. (10) Zou, X.; Zhang, Y. Noble Metal-Free Hydrogen Evolution Catalysts for Water Splitting. Chem. Soc. Rev. 2015, 44 (15), 5148–5180. https://doi.org/10.1039/C4CS00448E. 8 (11) McKone, J. R.; Marinescu, S. C.; Brunschwig, B. S.; Winkler, J. R.; Gray, H. B. EarthAbundant Hydrogen Evolution Electrocatalysts. Chem. Sci. 2014, 5 (3), 865–878. https://doi.org/10.1039/C3SC51711J. (12) Carmo, M.; Fritz, D. L.; Mergel, J.; Stolten, D. A Comprehensive Review on PEM Water Electrolysis. Int. J. Hydrog. Energy 2013, 38 (12), 4901–4934. https://doi.org/10.1016/j.ijhydene.2013.01.151. (13) Wang, Y.; Chen, K. S.; Mishler, J.; Cho, S. C.; Adroher, X. C. A Review of Polymer Electrolyte Membrane Fuel Cells: Technology, Applications, and Needs on Fundamental Research. Appl. Energy 2011, 88 (4), 981–1007. https://doi.org/10.1016/j.apenergy.2010.09.030. (14) Lubitz, W.; Ogata, H.; Rüdiger, O.; Reijerse, E. Hydrogenases. Chem. Rev. 2014, 114 (8), 4081–4148. https://doi.org/10.1021/cr4005814. (15) Jones, A. K.; Sillery, E.; Albracht, S. P. J.; Armstrong, F. A. Direct Comparison of the Electrocatalytic Oxidation of Hydrogen by an Enzyme and a Platinum Catalyst. Chem. Commun. 2002, No. 8, 866–867. https://doi.org/10.1039/B201337A. (16) Tian, X.; Zhao, P.; Sheng, W. Hydrogen Evolution and Oxidation: Mechanistic Studies and Material Advances. Adv. Mater. 2019, 31 (31), 1808066. https://doi.org/10.1002/adma.201808066. (17) Weber, A. Z.; Mench, M. M.; Meyers, J. P.; Ross, P. N.; Gostick, J. T.; Liu, Q. Redox Flow Batteries: A Review. J. Appl. Electrochem. 2011, 41 (10), 1137. https://doi.org/10.1007/s10800-011-0348-2. (18) Gong, K.; Fang, Q.; Gu, S.; Li, S. F. Y.; Yan, Y. Nonaqueous Redox-Flow Batteries: Organic Solvents, Supporting Electrolytes, and Redox Pairs. Energy Environ. Sci. 2015, 8 (12), 3515–3530. https://doi.org/10.1039/C5EE02341F. 9 (19) Potash, R. A.; McKone, J. R.; Conte, S.; Abruña, H. D. On the Benefits of a Symmetric Redox Flow Battery. J. Electrochem. https://doi.org/10.1149/2.0971602jes. Soc. 2016, 163 (3), A338–A344. 10 CHAPTER 2 KINETIC STUDIES OF HYDROGEN OXIDATION BY COBALOXIMES Introduction Cobaloximes as HER Catalysts Chart 1: Cobaloxime complexes. L is typically solvent or pyridine. In 1966, the first “cobaloximes” were synthesized by Schrauzer and Windgassen as models of the reduced form of vitamin B12, and they coined the term for this family of molecules by analogy to “cobalamin”.1 The reaction of dimethylglyoxime (usually abbreviated dmgH2) with cobaltous acetate resulted in the formation of a hydrogen-bonded macrocyclic complex, Co(dmgH)2L2, where the axial L sites are kinetically labile and usually occupied by solvent molecules. The remaining protons in the macrocycle can be replaced by BF2 on reaction with 11 BF3•Et2O,2 and the resulting complexes are generally much more stable, particularly in acid solution. Both reactions are quite general, and a number of similar complexes have been synthesized with varying substituents in the “backbone” of the diglyoxime macrocycle (Chart 1).3 Connolly and Espenson demonstrated in 1986 that trace amounts of Co(dmgBF2)2L2 catalyzed the evolution of H2 from acidic aqueous solutions of sufficiently reducing M(II) salts (M = Cr, Eu, V).4 They reported that the reaction slowed considerably in the absence of halide ions, leading them to conclude that the rate limiting step was inner-sphere electron transfer in a halide-bridged intermediate. Without rate-limiting H-H bond formation, the authors were unable to interrogate the mechanism of that step, and so they proposed two possible routes proceeding from a Co(III) hydride intermediate formed by the protonation of the reduced Co(I) form of the catalyst (Scheme 1, red and blue arrows). Scheme 1. Reproduced from reference 5 with permission from the copyright holder, American Chemical Society. This result was not further investigated until 2005, when both the Artero3 and Peters6 groups reported nonaqueous electrocatalytic proton reduction using cobaloxime catalysts. Artero and coworkers found that Co(dmgH)2(py)Cl electrocatalyzes HER from triethylammonium 12 chloride in DMF (pKa = 10.75) at the Co(II/I) couple (-0.98 V vs. Ag/AgCl). Notably, they report that substitution of BF2 for the bridging protons or H or Ph for the backbone methyls shifted the Co(II/I) couple anodically by ca. 100 mV, but shut down catalysis, suggesting that the Co(I) species formed were no longer basic enough to be protonated by triethylammonium. The authors considered the same general scheme as Connolly and Espenson, and concluded based on simulations of the cyclic voltammagrams that the heterolytic mechanism (Scheme 1, blue arrow) predominated under their catalytic conditions. In contrast, the Peters group found that the fluoroborated derivative Co(dmgBF2)2(MeCN)2 was a competent electrocatalyst for HER from trifluoroacetic acid (TFA) in MeCN (pKa = 12.7) at the Co(II/I) couple (-0.55 V vs. SCE). They also reported that the diphenylglyoxime congener Co(dpgBF2)2(MeCN)2 was a competent HER catalyst, but that the positive shift in the Co(II/I) couple relative to the methyl variant requires use of a stronger acid (HBF4•Et2O, pKa = 0.1) to maintain activity; neither complex showed activity when a weaker acid such as benzoic acid (pKa = 20.7) or TFA, respectively. Similar to Artero et al., Peters et al. used simulations of the catalytic cyclic voltammagrams to examine the mechanism of HER, but they concluded that the hemolytic mechanism (Scheme 1, red arrow) predominated for Co(dmgBF2)2(MeCN)2 and were unable to distinguish between the two mechanisms for Co(dpgBF2)2(MeCN)2. This pair of reports sparked a general interest in the use of cobaloximes for HER in a variety of contexts, including photocatalytic7–19 as well as electrocatalyic3,5,6,20 systems in both aqueous and organic solvents. Despite the ubiquity of these reports, however, a consensus mechanism never developed. There have been attempts to directly study the mechanism of cobaloxime-mediated HER, though the emerging picture has possibly become less clear rather than more. A 1971 report by Schrauzer and Holland21 identifying a “hydridocobaloxime” prepared by reduction with NaBH4 and stabilized by PBu3 trans to the hydride (Chart 2) has formed the basis for 13 mechanistic work from this apparent trapped intermediate. However, Artero et al. called into question the assignment of this complex as a classical metal hydride based on its purple color and the downfield 1H NMR resonance (~6 ppm) assigned as that of the hydride; a Co(III) hydride would be expected to be pale yellow with a hydride resonance upfield of 0 ppm.22 After repeating the experimental measurements and performing theoretical calculations, Artero reassigned the product as the ligand-protonated Co(I) tautomer of the original formulation with a hydride resonance of ~-5 ppm. Chart 2: Assignments of the structure of “hydridocobaloxime”. Top left, original assignment by Schrauzer and Holland;21 top right, reassignment by Artero et al.;22 bottom, major and minor products as assigned by Peters et al.23 More recently, the Peters group has again repeated that experimental characterization and found that the purple material which results from the NaBH4 reduction of Co(dmgH)2Cl(PBu3) does not correspond to a “hydridocobalxime” at all.23 Instead, the major product was confirmed by X-ray crystallography to be the Co-Co bonded dimer [Co(dmgH)2(PBu3)]2, with the apparent hydride signal arising from a paramagnetic trinuclear minor product. Alarmingly, this result invalidates mechanistic work which relied on this 14 incorrectly assigned “hydride”, including studies which measured the rate of H2 evolution from the material upon addition of acid24 as well as studies which assigned the spectra of various intermediates based on the spectrum of “hydridocobaloxime”.25 The most direct inspection of the mechanism of cobaloxime-mediated HER is a contribution from Dempsey and Gray in 2010 utilizing a strong photoacid and transient absorption spectroscopy to rapidly protonate [CoI(dmgBF2)2(MeCN)]-, allowing for the observation of the formation and decay of two intermediates prior to H2 evolution and generation of the Co(II).26 These intermediates were proposed to correspond first to the Co(III) hydride which results from protonation of the Co(I) anion, followed by the intermediate Co(II) hydride which results from reduction by excess Co(I). This final species is ultimately protonated again to release H2. This result demonstrated that further reduction of a Co(III) hydride is possible under catalytic conditions and may be necessary in order to render the metal hydride reactive enough to produce hydrogen. This pathway has more recently been proposed under electrocatalytic conditions based on foot-of-the-wave analysis and other electroanalytical chemistry methods.27,28 With this possibility under consideration, a second homolytic path (Scheme 1, violet arrow) may be added to the possibilities first proposed by Schrauzer. Also complicating the picture is the possibility for ligand noninnocence. The Peters group has investigated related macrocycles in which the oxime oxygens and bridging atoms on one half of the macrocycle have been replaced by hydrocarbon linkers (Chart 3), and these studies have highlighted the importance of ligand protonation in H-bridged cobaloxime systems.29 Aqueous HER catalysis by these complexes shows a Nernstian response consistent with a one-proton, one-electron process, while catalysis by Co(dmgBF2)2 complexes in MeCN does not, suggesting that protonation likely occurs on the ligand. 15 Chart 3: Cobalt diimine-dioxime complexes. Additionally, a report by the Norton group concerning high-pressure spectroscopy of Co(dmgBF2)2(MeCN)2 under 70 atm H2 features slow growth of optical and 1H NMR spectral features consistent with a solvent-assisted ligand-protonated product, suggesting that a ligand-protonated species could figure into catalysis even in the fluoroborated cobaloximes.30 Electrochemical analysis of Co(dmgBF2)2(MeCN)2 under high pressures of H2, however, cast doubt on this hypothesis, as the CoII/I couple is positioned ca. 300 mV more negative than at 1 atm, which suggests that ligand-protonated species would not be the observed catalyst even if it is generated.27 Figure 1: Proposed structure of the high-pressure reaction between H2 and Co(dmgBF2)2(MeCN)2 (L = MeCN). History of Cobaloximes as Hydrogenation and HOR Catalysts In the 1970s, the Simándi and Yamaguchi groups reported the first reactions of cobaloximes with dihydrogen, which resulted in decomposition via hydrogenation of the macrocyclic ligand.31–34 This decomposition can be outcompeted by catalytic hydrogenation if an 16 alternate substrate such as a Schiff base35 or styrene32 is present. Simándi et al. reported that the rate law for hydrogenation of styrene in MeOH and 1:1 MeOH:H2O is second-order in Co(dmgH)2 and first-order in H2, suggesting that the turnover-limiting step is homolytic activation of H2. They also reported that coordination of an axial pyridine in lieu of solvent (MeOH/H2O) enhanced the reaction rate by two orders of magnitude, highlighting the importance of understanding the effect of the axial ligands in cobaloxime systems. Complicating the matter, under most conditions the resting state of the cobaloxime is Co(II), a labile oxidation state that lends the molecule to readily undergo axial ligand substitution, leading to speciation if more than one viable ligand exists in solution.36 Similar axial ligand effects have surfaced in more recent years in both the HER12,37,38 and H2 activation39 literature. Simándi et al. also studied the reaction of Co(dmgH)2 complexes with H2 in the presence of strong Brønsted base and found it competent for HOR catalysis.31 As with styrene, the observed rate law is termolecular, but the HOR rate is enhanced relative to styrene hydrogenation, which implies that they cannot have the same intermediate in the rate-limiting step. Simándi et al. propose that deprotonation of one of the macrocyclic bridges produces a more active species for H2 activation, a suggestion which mirrors more recent observations of ligand protonation in HER. Norton et al. have more recently developed Co(dmgBF2)2 complexes under H2 as H-atom transfer catalysts for radical cyclizations.40 Kinetics experiments with a modified trityl radical and with TEMPO as H-atom acceptors resulted in a rate law second-order in Co, firstorder in H2, and independent of acceptor concentration or identity. This result suggests that substitution of BF2 at the bridging position does not change the turnover-limiting H2 activation found by Simándi et al. Further detailed mechanistic work from the Norton group has established that only the pentacoordinate Co(dmgBF2)2L is active, and that the identity of L can have a dramatic effect on the rate of reaction.39 Stronger donor ligands which labilize the trans ligand can case as much as an order of magnitude rate enhancement. By contrast, the rate is slowed by an order of magnitude by PPh3, which only singly ligates 17 Co(dmgBF2)2, which they attribute to enforcement of a pseudo-boat conformation in the macrocycle rather than the pseudo-chair observed in most crystal structures. The pseudoboat conformation may be sterically congested enough to slow bimolecular activation of H2. Studies of HOR in organic solvent with fluoroborated cobaloximes have been limited to a stoichiometric demonstration by the Peters group that with Co(dmgBF2)2(MeCN)2, but not Co(dpgBF2)2(MeCN)2, some degree of reversibility is possible using the conjugate bases of the acids used for HER catalysis.20 The reaction approaches an unfavorable (Keq = 0.03 atm1/2 ) equilibrium over the course of 34 with anisosbestic behavior, which the authors attribute to decomposition of the complex. Taken together, these reports display that the rate cobaloxime-mediated H2 activation in both HOR and hydrogenation reactions are markedly sensitive to changes in both the macrocycle and axial ligands. The third-order rate constants found by Simándi et al. range from ~103200 M-2s-1 for styrene hydrogenation by Co(dmgH)2, depending on the solvent and presence of added pyridine.32 When the reaction is instead HOR with strong base, they found a thirdorder rate constant of ~2200 M-2s-1.31 In MeCN, Norton et al. found a third-order rate constant of ~110 M-2s-1 for radical hydrogenation.40 This relatively slow oxidation of H2 in acetonitrile contrasts with the fast second-order rates (kapp = 7000 M-1s-1) observed for Co(dmgBF2)2(MeCN)2-catalyzed HER.6 Additional research is needed to clarify the mechanism of cobaloxime-mediated HER and HOR and the factors governing the reaction rates. 18 Results Scheme 2 The stoichiometric oxidation of hydrogen to protons by cobaloximes may proceed either via bimetallic homolytic H-H bond cleavage or deprotonation (heterolysis), and the balance of data in the literature suggests that both pathways are accessible (Scheme 2). Using the preequilibrium approximation for equations (1) and (3) and the steady-state approximation for [CoIII-H], a rate law emerges which is second-order in Co regardless of the dominant pathway (Equation 6). In this work, kinetic studies of Co(dmgBF2)2L2-mediated HOR were undertaken with the goal of determining whether this approximate rate law is appropriate and, if so, to measure the rate constants related to each pathway. By better understanding the bifurcation between these two pathways, insight may be gained into the microscopic-reverse HER. (6) 𝑑𝑑[𝐶𝐶𝐶𝐶𝐼𝐼 ]− [𝐵𝐵] = �𝐾𝐾1 𝑘𝑘2 + 𝐾𝐾1 𝐾𝐾3 𝑘𝑘4 � [𝐶𝐶𝐶𝐶𝐼𝐼𝐼𝐼 ]2 [𝐻𝐻2 ] + 𝑑𝑑𝑑𝑑 [𝐻𝐻𝐻𝐻 ] 19 Selection of Base and Initial Kinetic Experiments Co(II) species are kinetically labile, and cobaloximes in this oxidation state rapidly exchange axial ligands. In order to simplify kinetic analysis and avoid solution speciation, a noncoordinating base was sought which would ensure that solvent was the only source of spectator axial ligands. The optical spectra of Co(dmgBF2)2(MeCN)2 solutions in MeCN were not altered by addition of N,N-dimethylaniline or 1,8-bis(dimethylamino)naphthalene (“proton sponge”), indicating neither displaces axial MeCN. Proton sponge is a relatively strong base (conjugate acid pKa in MeCN = 18.241), which favors the products side of the equilibrium, and an easy-to-handle solid at room temperature, making it an ideal candidate for initial studies. Addition of an atmosphere of H2 to a MeCN solution containing Co(dmgBF2)2(MeCN)2 and excess proton sponge resulted in the appearance of optical bands at 553 and 628 nm, consistent with the known spectrum of [Co(dmgBF2)2MeCN]- after an induction period of three hours (Figure 2).26 The [Co(dmgBF2)2MeCN]- spectrum continued to grow in isosbestically over the course of three days until all of the Co(dmgBF2)2(MeCN)2 had been converted to [Co(dmgBF2)2MeCN]-. The reaction did not reverse when the H2 atmosphere was removed and was not altered by the presence of the conjugate acid. 20 Figure 2: Time-dependent optical spectra of 1.9 mM Co(dmgBF2)2(MeCN)2 and 36 mM proton sponge in MeCN under 1 atm H2. Figure 3: Concentration of Co(I) over time based on absorption at 553 nm. 21 Varying the concentration of both the Co species and the base produced variable induction periods with no distinct pattern, but all reactions proceeded to completion over the course of 2-3 days. Plots of the natural logarithm, inverse, and inverse-square of concentration vs. time were all nonlinear even when the induction period was excluded from the data. Figure 4: Comparison of data from runs with different initial concentrations of Co(dmgBF2)2(MeCN)2 (Co) and proton sponger (PS). Initial Rate Experiments Using Proton Sponge The initial rate method is ideal for studying slow reactions, and was pursued along with higher concentration experiments to expedite data collection (Table 1, additional data in Supporting Data). The initial concentration of each reactant was systematically varied, and the average of a linear fit of the absorption data for the two Co(I) bands used to calculate the initial rate for each condition, truncating any observed induction period. The initial rate was not affected by variations in initial concentration of proton sponge. However, doubling the 22 initial pressure of H2 resulted in a doubling of the initial rate, and the initial rate varied with variations in the initial concentration of Co(dmgBF2)2(MeCN)2. A natural log-log plot of the initial rate vs. concentration was linear with a slope of 2.03 (Figure 5). Table 1: Initial rate data for the reaction of Co(dmgBF2)2(MeCN)2 (Co), proton sponge (B) and H2. Entry [Co]0 (mM) [B]0 (mM) P(H2) (atm) Initial Rate (M/s x 107) 1 5.8 8.5 1.0 3.4 2 6.0 4.3 1.0 3.3 3 6.0 2.1 1.0 3.2 4 4.6 2.2 1.0 1.9 5 3.0 2.1 1.0 0.91 6 1.7 2.2 1.0 0.23 7 5.8 25.2 1.0 4.4 8 6.2 19.7 0.50 1.9 9 6.3 19.7 0.25 0.86 23 Figure 5: Rate vs. concentration log-log plot for Co-varied runs and fit line. Slope = 2.03, R2 = 0.999. Extension to N,N-dimethylaniline Further initial rate experiments were pursued using N,N-dimethylaniline in order to understand the effect of base strength (conjugate acid pKa in MeCN = 11.442) on the kinetics of Co(dmgBF2)2(MeCN)2-mediated HOR. Induction periods prior to the appearance of [Co(dmgBF2)2MeCN]- bands were frequently observed. The concentration vs. time data became nonlinear within minutes, and the reaction did not proceed to completion after 24 h. After three days, the solution had reached equilibrium with an equilibrium constant of 1.3 x 10-5 atm-1/2. Removal of H2 resulted in a slow diminution of the [Co(dmgBF2)2MeCN]spectrum. 24 Figure 6: Example plots of absorbance over time for Co(dmgBF2)2(MeCN)2 and N,N-dimethylaniline under H2. Discussion Observed Induction Period The variable induction periods observed in these experiments likely occur due to trace O2 present in solution. Blue solutions of [Co(dmgBF2)2MeCN]- are rapidly converted to yellow Co(dmgBF2)2(MeCN)2 on exposure to air, and the induction periods observed were considerably longer when an ordinary Schlenk line (pressure ca. 50 mTorr) was used to degas the reaction vessel than when a high vacuum line (pressure ca. 5 μTorr) was used. The induction period is then produced by rapid reoxidation of [Co(dmgBF2)2MeCN]- as it is produced at early time points. If this is the case, initial rate data recorded after the induction period ends should still be valid, since the reaction of interest is rate-limiting and therefore the induction period is simply obscuring the beginning of the linear data region. However, rigorous exclusion of oxygen or monitoring of the production of products not affected by trace oxygen (i.e. conjugate acid) would be desirable to verify this hypothesis and ensure the reliablility of the data collected. Additionally, for experiments with bases such as N,Ndimethylaniline which approach equilibrium rapidly relative to the length of the induction 25 period, enough of the linear data region may be obscured to render initial rates difficult to reliably extract. The source of the O2 is unclear, as solutions were prepared in a nitrogen-filled glovebox in Kontes valve-equipped cuvettes which were sufficiently gastight to prevent detectable leakage of H2 and degassed on a high-vacuum line before H2 addition from a line flushed with gas for several minutes. These conditions would ordinarily be considered rigorously free of O2; it is possible that this reaction is simply slow enough to observe the effects of unavoidable traces of O2 which remain despite the most rigorous efforts to eliminate it. Rate Law of HOR The initial rate data for Co(dmgBF2)2(MeCN)2-mediated HOR indicates a reaction that is second-order in Co, first-order in H2, and zero-order in proton sponge, with a rate constant of 3.8 ± .5 M-2s-1. This rate law suggests that only the homolytic pathway is accessed in this reaction, and the rate constant is smaller by two orders of magnitude than that measured by Norton with radical scavengers.40 The complete dominance of the homolytic pathway is unexpected, given that proton sponge is sufficiently basic to make the reaction irreversible, as evidenced by the final concentration of [Co(dmgBF2)2MeCN]- being equal to the initial concentration of Co(dmgBF2)2(MeCN)2, the observation that the reaction does not reverse when the H2 atmosphere is removed, and the lack of any effect on the reaction when the conjugate acid is present in solution. It is possible, then, that the pKa of the Co(III) hydride species is less than 18.2 in MeCN, but the pKa of the dihydrogen adduct is much higher. Recent work examining the relationship between acid identity and hydride formation rates in a related Co complex identified a departure from the linear free energy relationship with pKa when the acidic proton is sterically encumbered, as in N,N-dimethylanilinium.43 It is therefore also possible that the selection of a sterically encumbered base in order to preclude solution speciation has resulted 26 in a much slower deprotonation rate than would be expected based on pH, to the point where heterolysis cannot compete with homolysis. Further research would be needed to distinguish these effects. Alternate strategies for circumventing solution speciation, such as using a strong non-solvent axial ligand to push the speciation equilibrium far to one side or operating in a noncoordinating solvent such as CH2Cl2 would allow for unencumbered bases to be examined and analyzed unambiguously based on conjugate acid pKa. Conclusion Initial rate data suggests that the HOR mediated by Co(dmgBF2)2(MeCN)2 using proton sponge as the base proceeds by homolytic cleavage of the H-H bond. More experiments varying the base are needed to contextualize these results, as well as better methodology with respect to the exclusion of oxygen. References (1) Schrauzer, G. N.; Windgassen, R. J. Über Cobaloxime(II) Und Deren Beziehung Zum Vitamin B12r. Chem. Ber. 1966, 99 (2), 602–610. https://doi.org/10.1002/cber.19660990234. (2) Schrauzer, G. N.; Windgassen, R. J. Alkylcobaloximes and Their Relation to Alkylcobalamins. J. Am. Chem. Soc. 1966, 88 (16), 3738–3743. https://doi.org/10.1021/ja00968a012. (3) Razavet, M.; Artero, V.; Fontecave, M. Proton Electroreduction Catalyzed by Cobaloximes: Functional Models for Hydrogenases. Inorg. Chem. 2005, 44 (13), 4786– 4795. https://doi.org/10.1021/ic050167z. (4) Connolly, P.; Espenson, J. H. Cobalt-Catalyzed Evolution of Molecular Hydrogen. Inorg. 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W.; Eisenberg, R. Visible Light-Driven Hydrogen Production from Aqueous Protons Catalyzed by Molecular Cobaloxime Catalysts. Inorg. Chem. 2009, 48 (11), 4952–4962. https://doi.org/10.1021/ic900389z. (20) Hu, X.; Brunschwig, B. S.; Peters, J. C. Electrocatalytic Hydrogen Evolution at Low Overpotentials by Cobalt Macrocyclic Glyoxime and Tetraimine Complexes. J. Am. Chem. Soc. 2007, 129 (29), 8988–8998. https://doi.org/10.1021/ja067876b. (21) Schrauzer, G. N.; Holland, R. J. Hydridocobaloximes. J. Am. Chem. Soc. 1971, 93 (6), 1505–1506. https://doi.org/10.1021/ja00735a040. (22) Bhattacharjee, A.; Chavarot-Kerlidou, M.; Andreiadis, Eugen. S.; Fontecave, M.; Field, M. J.; Artero, V. Combined Experimental–Theoretical Characterization of the HydridoCobaloxime [HCo(DmgH)2(PnBu3)]. Inorg. Chem. 2012, 51 (13), 7087–7093. https://doi.org/10.1021/ic2024204. (23) Lacy, D. C.; Roberts, G. M.; Peters, J. C. The Cobalt Hydride That Never Was: Revisiting Schrauzer’s “Hydridocobaloxime.” J. Am. Chem. Soc. 2015, 137 (14), 4860– 4864. https://doi.org/10.1021/jacs.5b01838. (24) Chao, T.-H.; Espenson, J. H. Mechanism of Hydrogen Evolution from Hydridocobaloxime. J. Am. Chem. Soc. 1978, 100 (1), 129–133. https://doi.org/10.1021/ja00469a022. (25) Szajna‐Fuller, E.; Bakac, A. Catalytic Generation of Hydrogen with Titanium Citrate and a Macrocyclic Cobalt Complex. Eur. J. Inorg. Chem. 2010, 2010 (17), 2488–2494. https://doi.org/10.1002/ejic.200901176. (26) Dempsey, J. L.; Winkler, J. R.; Gray, H. B. Mechanism of H2 Evolution from a Photogenerated Hydridocobaloxime. J. Am. Chem. Soc. 2010, 132 (47), 16774–16776. https://doi.org/10.1021/ja109351h. 30 (27) Wiedner, E. S.; Bullock, R. M. Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production. J. Am. Chem. Soc. 2016, 138 (26), 8309–8318. https://doi.org/10.1021/jacs.6b04779. (28) Rountree, E. S.; Martin, D. J.; McCarthy, B. D.; Dempsey, J. L. Linear Free Energy Relationships in the Hydrogen Evolution Reaction: Kinetic Analysis of a Cobaloxime Catalyst. ACS Catal. 2016, 6 (5), 3326–3335. https://doi.org/10.1021/acscatal.6b00667. (29) McCrory, C. C. L.; Uyeda, C.; Peters, J. C. Electrocatalytic Hydrogen Evolution in Acidic Water with Molecular Cobalt Tetraazamacrocycles. J. Am. Chem. Soc. 2012, 134 (6), 3164–3170. https://doi.org/10.1021/ja210661k. (30) Estes, D. P.; Grills, D. C.; Norton, J. R. The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics. J. Am. Chem. Soc. 2014, 136 (50), 17362–17365. https://doi.org/10.1021/ja508200g. (31) Simándi, L. I.; Budó-Záhonyi, É.; Szeverényi, Z. Effect of Strong Base on the Activation of Molecular Hydrogen by Pyridinebis(Dimethylglyoximato)Cobalt(II). Inorg. Nucl. Chem. Lett. 1976, 12 (3), 237–241. https://doi.org/10.1016/0020-1650(76)80158-4. (32) Simándi, L. I.; Szeverényi, Z.; Budó-Záhonyi, É. Activation of Molecular Hydrogen by Cobaloxime(II) Derivatives. Inorg. Nucl. Chem. Lett. 1975, 11 (11), 773–777. https://doi.org/10.1016/0020-1650(75)80098-5. (33) Yamaguchi, T.; Miyagawa, R. The Effect of Pyridine on the Hydrogen Absorption Process of Bis(Dimethylglyoximato)Cobalt(Ii). Chem. Lett. 1978, 7 (1), 89–92. https://doi.org/10.1246/cl.1978.89. (34) Yamaguchi, T.; Tsumura, T. The Effect of Triphenylphosphine on the Hydrogenation Reaction of Bis(Dimethylglyoximato)Cobalt(Ii). Chem. Lett. 1973, 2 (4), 409–412. https://doi.org/10.1246/cl.1973.409. 31 (35) Yamaguchi, T.; Nakayama, M.; Tsumura, T. The Effect of Base Strength of Schiff Bases on Their Catalytic Hydrogenation with Bis(Dimethylglyoximato)Cobalt(Ii). Chem. Lett. 1972, 1 (12), 1231–1234. https://doi.org/10.1246/cl.1972.1231. (36) Lawrence, M. A. W.; Celestine, M. J.; Artis, E. T.; Joseph, L. S.; Esquivel, D. L.; Ledbetter, A. J.; Cropek, D. M.; Jarrett, W. L.; Bayse, C. A.; Brewer, M. I.; et al. Computational, Electrochemical, and Spectroscopic Studies of Two Mononuclear Cobaloximes: The Influence of an Axial Pyridine and Solvent on the Redox Behaviour and Evidence for Pyridine Coordination to Cobalt(I) and Cobalt(II) Metal Centres. Dalton Trans. 2016, 45 (25), 10326–10342. https://doi.org/10.1039/C6DT01583B. (37) Basu, D.; Mazumder, S.; Niklas, J.; Baydoun, H.; Wanniarachchi, D.; Shi, X.; Staples, R. J.; Poluektov, O.; Schlegel, H. B.; Verani, C. N. Evaluation of the Coordination Preferences and Catalytic Pathways of Heteroaxial Cobalt Oximes towards Hydrogen Generation. Chem. Sci. 2016, 7 (5), 3264–3278. https://doi.org/10.1039/C5SC04214C. (38) Panagiotopoulos, A.; Ladomenou, K.; Sun, D.; Artero, V.; Coutsolelos, A. G. Photochemical Hydrogen Production and Cobaloximes: The Influence of the Cobalt Axial N-Ligand on the System Stability. Dalton Trans. 2016, 45 (15), 6732–6738. https://doi.org/10.1039/C5DT04502A. (39) Li, G.; Estes, D. P.; Norton, J. R.; Ruccolo, S.; Sattler, A.; Sattler, W. Dihydrogen Activation by Cobaloximes with Various Axial Ligands. Inorg. Chem. 2014, 53 (19), 10743– 10747. https://doi.org/10.1021/ic501975r. (40) Li, G.; Han, A.; Pulling, M. E.; Estes, D. P.; Norton, J. R. Evidence for Formation of a Co–H Bond from (H2O)2Co(DmgBF2)2 under H2: Application to Radical Cyclizations. J. Am. Chem. Soc. 2012, 134 (36), 14662–14665. https://doi.org/10.1021/ja306037w. (41) Ozeryanskii, V. A.; Pozharskii, A. F.; Milgizina, G. R.; Howard, S. T. Synthesis and Properties of 5,6-Bis(Dimethylamino)Acenaphthylene: The First Proton Sponge with Easily-Modified Basicity. J. https://doi.org/10.1021/jo001171p. Org. Chem. 2000, 65 (22), 7707–7709. 32 (42) Tshepelevitsh, S.; Kütt, A.; Lõkov, M.; Kaljurand, I.; Saame, J.; Heering, A.; Plieger, P. G.; Vianello, R.; Leito, I. On the Basicity of Organic Bases in Different Media. Eur. J. Org. Chem. 2019, 2019 (40), 6735–6748. https://doi.org/10.1002/ejoc.201900956. (43) Elgrishi, N.; Kurtz, D. A.; Dempsey, J. L. Reaction Parameters Influencing Cobalt Hydride Formation Kinetics: Implications for Benchmarking H2-Evolution Catalysts. J. Am. Chem. Soc. 2017, 139 (1), 239–244. https://doi.org/10.1021/jacs.6b10148. (44) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Safe and Convenient Procedure for Solvent Purification. Organometallics 1996, 15 (5), 1518– 1520. https://doi.org/10.1021/om9503712. 33 Methods General Considerations Unless stated otherwise, all manipulations were carried out in a nitrogen-filled glovebox or under nitrogen or argon using standard Schlenk techniques. Dry, air-free solvents were obtained from a Grubbs-type solvent purification system.44 Co(dmgBF2)2(MeCN)2 was synthesized by a literature method26 and its purity confirmed by cyclic voltammetry prior to use. Proton sponge and N,N-dimethylaniline were ordered from Sigma-Aldrich and used as received. UV-Vis spectra were recorded on a Cary Bio 50 spectrometer. General Procedure for Kinetics Experiments A solution of Co(dmgBF2)2(MeCN)2 and base (proton sponge or N,N-dimethylaniline) was prepared in MeCN. A 1 mm path length, Kontes valve-sealed cuvette equipped with a sidearm bulb and a stirbar was charged with the solution and degassed on a high-vacuum line by the freeze-pump-thaw method twice. The solution was allowed to warm to room temperature before H2 was added to the desired pressure. The reaction was monitored by UV-Vis spectroscopy by tipping the solution into the cuvette at the desired intervals and was stirred in the side-arm bulb between spectra. 34 Supporting Data Figure S1: Initial rate plot for Table 1 entry 1, calculated based on absorbance at 553 nm. Figure S2: Initial rate plot for Table 1 entry 1, calculated based on absorbance at 628 nm. 35 Figure S3: Initial rate plot for Table 1 entry 2, calculated based on absorbance at 553 nm. Figure S4: Initial rate plot for Table 1 entry 2, calculated based on absorbance at 628 nm. 36 Figure S5: Initial rate plot for Table 1 entry 3, calculated based on absorbance at 553 nm. Figure S6: Initial rate plot for Table 1 entry 3, calculated based on absorbance at 628 nm. 37 Figure S7: Initial rate plot for Table 1 entry 4, calculated based on absorbance at 553 nm. Figure S8: Initial rate plot for Table 1 entry 4, calculated based on absorbance at 628 nm. 38 Figure S9: Initial rate plot for Table 1 entry 5, calculated based on absorbance at 553 nm. Figure S10: Initial rate plot for Table 1 entry 5, calculated based on absorbance at 628 nm. 39 Figure S11: Initial rate plot for Table 1 entry 6, calculated based on absorbance at 553 nm. Figure S12: Initial rate plot for Table 1 entry 6, calculated based on absorbance at 628 nm. 40 Figure S13: Initial rate plot for Table 1 entry 7, calculated based on absorbance at 553 nm. Figure S14: Initial rate plot for Table 1 entry 7, calculated based on absorbance at 628 nm. 41 Figure S15: Initial rate plot for Table 1 entry 8, calculated based on absorbance at 553 nm. Figure S16: Initial rate plot for Table 1 entry 8, calculated based on absorbance at 628 nm. 42 Figure S17: Initial rate plot for Table 1 entry 9, calculated based on absorbance at 553 nm Figure S18: Initial rate plot for Table 1 entry 9, calculated based on absorbance at 628 nm. 43 CHAPTER 3 SYNTHESIS, SPECTROSCOPY AND BORONATION OF A NEW HETEROLEPTIC RUTHENIUM CYANIDE COMPLEX Introduction [Ru(diimine)(CN)4] 2- complexes Figure 1: Structure of [Ru(bpy)(CN)4]2-. Inspired by mounting evidence that the long-lived metal-to-ligand charge transfer (MLCT) excited state of [Ru(bpy)3]2+ featured an electron localized on just one bpy ligand, Scandola et al. first synthesized [Ru(bpy)(CN)4]2- (Figure 1) in 1986 as a minimalistic model of Ru(II) diimine photosensitizers.1 They observed that the luminescence and excited-state properties were very similar to [Ru(bpy)3]2+, but that the spectroscopic properties also featured strong solvatochromism. The magnitude of 44 the solvatochromism is driven largely by specific solvent interactions with the cyanide ligands. In a systematic study of Ru-polypyridyl-cyanide complexes with 15 cyanides, Meyer et al. found that shifts in the C-N stretching frequency, MLCT absorption energy, and emission energy all correlated with the Gutmann acceptor number of the solvent and increased as a function of the number of cyanide ligands.2 These solvatochromic properties have driven much of the interest in [Ru(bpy)(CN)4]2- and related [Ru(diimine)(CN)4]2- complexes,3–5 and several applications have been reported. PPN2 Ru(bpy)(CN)4 (PPN = bis(triphenylphosphine)iminium) can be used as a humidity sensor, as it reversibly turns from purple to yellow on exposure to water vapor.6 Solvent-tunable dye sensitized solar cells have been produced using a carboxylate-modified bpy to append the molecule to TiO2.7 The exposed lone pair on the cyanide nitrogen in [Ru(diimine)(CN)4]2- complexes has also been exploited to form supramolecular assemblies through hydrogen bonding8–13 or coordination to other metal centers.14–21 These assemblies often have interesting luminescence or energy-transfer properties, and one such assembly has been exploited as a sensor and chemodosimeter for amines released during food spoilage.15,16 Borane Modification of Metal Cyanide Complexes In 1963, Shriver observed that a number of cyanometallates could absorb an equivalent of borane per cyanide, resulting in a ca. 100 cm-1 shift in the C-N stretch to higher frequencies.22 For the homoleptic cyanometallates, he found that the d-d transitions were unaffected by the coordination of borane, but the spectrum of Fe(phen)2(CN)2, which is dominated by MLCT transitions, blueshifted dramatically. This pair of observations indicates that formation of the borane adduct stabilizes metal-centered orbitals, but has no strong effect on the ligand-based orbitals. As a 45 result, one expects that d-d transitions should remain relatively constant, MLCT transitions should blueshift, and ligand-to-metal charge transfer (LMCT) transitions should redshift on boronation; electrochemically, the same orbital shifts should produce anodic shifts in metal-centered redox processes while minimally affecting ligand-centered redox processes. While this area of research had been fairly dormant since Shriver’s work, it became of interest to the Gray group as a way of tuning the potential of cyanometallates in order to produce high-voltage redox flow battery electrolytes. As expected, McNicholas et al. found that addition of boranes to ferricyanide anodically shift the FeII/III couple.23 By examining cyclic voltammagrams containing substoichiometric BPh3, which coordinates reversibly to the cyanides, they determined that there is a linear relationship between the number of boranes coordinated and the magnitude of the shift. Each equivalent of BPh3 shifts the ferricyanide couple by ca. 260 mV, and for BCF, which coordinates irreversibly, a more dramatic 350 mV shift was observed. These observations were in line with previous publications which showed similar shifts in OsII/III 24 and ReI/II couples25 on addition of the same boranes to cyanide ligands. As of this writing, the study of boronation of homoleptic cyanometallates is very active within the Gray group, and manuscripts are now in preparation describing synthesis and spectroscopy of Co, Mn, Cr, Fe, Ru, Os, Ni, and Pt isocyanoborate complexes.26–28 Previous Work on Boronation of [Ru(bpy)(CN)4] 2- and related complexes In an effort to develop symmetric redox flow battery electrolytes, the boronation of Fe(II) and Ru(II) cyanometallates containing bpy and phen has also been studied recently in the Gray group.26,29 [Ru(bpy)(CN)4]2-, [Fe(bpy)(CN)4]2-, and [Fe(phen)(CN)4]2- were each boronated with both BPh3 and BCF. In each case, 46 boronation produces a shift to higher frequency of the C-N stretches, a blueshift in the MLCT-dominated optical spectrum, and an anodic shift of the MII/III couple, with more dramatic shifts for BCF than BPh3, reflecting its higher Lewis acidity. In the case of [Ru(bpy)(CN)4]2--, boronation also results in a luminescent excited state that is two orders of magnitude longer-lived, although the BPh3 adduct undergoes photodecomposition with loss of the borane. Although a redox flow battery has not yet been successfully created from it, this research resulted in the synthesis of [Ru(bpy)(CN-BCF)4]2--, which in MeCN has two reversible redox events separated by more than 3.5 V. This voltage would greatly improve upon the working voltages of existing flow battery systems. The following work represents an effort to improve the reductive stability of this molecule. Results & Discussion Synthesis and Spectroscopy of [Ru(CF3bpy)(CN)4] 2K2Ru(CF3bpy)(CN)4 (CF3bpy = 4,4’-bis(trifluoromethyl)-2,2’-bipyridine) was synthesized analogously to other K2Ru(diimine)(CN)4 complexes30 and converted to the PPN salt by precipitation from aqueous solution. PPN2Ru(CF3bpy)(CN)4 is received initially as a brick-red solid which is soluble in polar organic solvents and turns dark green when fully dehydrated. The complex was characterized by 1H and 19 F NMR spectroscopy, solid-state IR spectroscopy, elemental analysis, and X-ray crystallography. 47 Figure 2: Molecular structure of PPN2Ru(CF3bpy)(CN)4. Thermal ellipsoids set at 50% probability. Cations, hydrogen atoms, and solvent molecules omitted for clarity. The X-ray crystallographic data (Figure 2) reveals a negligible difference in metalligand contacts between [Ru(CF3bpy)(CN)4]2- and the parent bpy complex,6 which suggests that there is minimal difference in backbonding, despite the more electrondeficient bipyridine ligand. The C-N stretches detected in the solid state by FT-IR spectroscopy (Figure 3) support this interpretation. Typical complexes in this family have three closely-spaced strong peaks between 2030-2060 cm-1 and a weaker peak around 2090 cm-1; the closely-spaced peaks were not resolved, but the observed peaks at 2062 and 2090 cm-1 are in line with related complexes. 48 Figure 3: IR spectrum of PPN2Ru(CF3bpy)(CN)4 with CN stretches highlighted in inset. 49 Figure 4: UV-Vis spectra of [Ru(CF3bpy)(CN)4]2- in water (red broken trace, K salt) and acetonitrile (green solid trace, PPN salt). [Ru(diimine)(CN)4]2- complexes are well-known for their solvatochromism, which results both from having a ground-state dipole which interacts with polar solvents and the ability to accept hydrogen bonds at the N-termini of the cyanide ligands.5 Likewise, [Ru(CF3bpy)(CN)4]2- displays strong solvatochromism, with the lowestenergy MLCT transition redshifting ca. 5500 cm-1 when the solvent is changed from water to acetonitrile (Figure 4). In water, the spectrum displays three distinct bands, which can be assigned as two MLCT transitions and a CF3bpy-based π-π* transition based on their extinction coefficients (~103 M-1cm-1 for MLCT transitions and ~104 for π-π*). Both MLCT transitions are dramatically shifted by the change in solvent, but the π-π* transition shifts only slightly (ca. 550 cm-1), indicating that cyanide lone pair interactions are able to shift the d(Ru) orbitals while minimally affecting the 50 CF3 bpy orbitals. The absorption bands are also redshifted relative to most other [Ru(diimine)(CN)4]2- complexes (Table 1), reflecting the low-lying π orbitals of CF3 bpy relative to bpy and other commonly-used diimines. In this respect, CF3bpy displays similar electronic properties to bpz, but without the exposed lone pairs which hydrogen bond with water. Table 1: Comparison of room temperature photophysical and selected data for [Ru(CF3bpy)(CN)4]2[Ru(diimine)(CN)4]2- complexes. Rbpy indicates R in the 4,4’ positions of bipyridine. Diimine ligand Solvent λmax (nm)(ε (M-1 cm-1)) λem (nm) (τ (ns)) Reference bpy bpy Me bpym bpz bpy HOOC bpy CF3 H2O 400 610(101) 1 H2O 404(4100) 624(100) 11 MeCN 535 790(7) 8 H2O 392 600(115) 31 MeCN 530 780(7) 31 D2O 437(2200) (3.4) 19 MeCN 575 (0.25) 19 H2O 465(5700) 704(5) 32 MeCN 554 MeCN 515 750 7 H2O 443(3170) 706 This work MeCN 589(3770) N.O. below 930 This work 32 While [Ru(diimine)(CN)4]2- displays weak luminescence in aqueous solution (Figure S6), no luminescence was observed in the solid state or 2-MeTHF solution at room temperature or 77 K, suggesting that the emission in the dehydrated form may be redshifted beyond the 930 nm detection limit of the instruments used. 51 Figure 5: Cyclic voltammagram of 33 mM PPN2 Ru(CF3bpy)(CN)4 in 0.2 M Bu4NPF6-supported acetonitrile. Working electrode: glassy carbon. Counter electrode: Pt wire. The cyclic voltammagram of PPN2 Ru(CF3bpy)(CN)4 in 0.2 M Bu4NPF6-supported acetonitrile displays two redox events at 0.05 and -1.92 V vs. Fc+/0 corresponding to oxidation of the metal center to Ru(III) and reduction of the CF3 bpy ligand, respectively (Figure 5). The peak current ratios for both waves are close to unity and the peak-to-peak separations are ca. 79 mV and independent of scan rate, indicating diffusion-controlled reversible electron transfer. While the parent bpy complex features a second irreversible reduction presumed to be deligation of bpy2-,33 no such reduction or decomposition is observed for [Ru(CF3bpy)(CN)4]2-. The reductive stability of CF3bpy in this system is accompanied by a 330 mV anodic shift in the bpy0/- couple relative to the parent complex and a 230 mV anodic shift in the Ru2+/3+ 52 couple. These shifts indicate that not only is CF3bpy more easily reduced than bpy, but that inductive effects result in a harder to oxidize Ru center. Boronation with BCF and Spectroscopy The tris(pentafluorophenyl)borane (BCF) adduct PPN2 Ru(CF3bpy)(CN-BCF)4 was prepared in inert atmosphere by mixing DCM solutions of PPN2 Ru(CF3bpy)(CN)4 and BCF and heating. On addition of the colorless BCF solution, the dark green PPN2 Ru(CF3bpy)(CN)4 solution rapidly turns yellow. The resulting complex is an airstable, luminescent yellow solid which is extremely soluble in polar organic solvents and has been characterized by 1H, 19F, and 11B NMR spectroscopy, solid state IR spectroscopy, elemental analysis, and X-ray crystallography. Figure 6: Molecular structure of PPN2 Ru(CF3bpy)(CNBCF)4. Thermal ellipsoids set at 50% probability. Cations, hydrogen and fluorine atoms, and solvent molecules omitted for clarity. 53 On addition of the borane, there is negligible change in the C-N distances and only a small shortening (ca. 0.05 Å) of the Ru-C distances (Figure 6). This observation is in line with the trends observed on addition of BCF to ferricyanide,23 and likely results from a balancing of the bond-lengthening effect of N-donation to the borane and the bond-shortening effect of increased backbonding from Ru to the more π- acidic isocyanoborate. Crystallization of the related heteroleptic borane adducts has been stymied by their high solubility,26,29 so more direct comparisons are not currently possible. Presumably due to steric crowding, the axial isocyanoborate ligands bow significantly (Ru-C-N bond angle 170°) over the plane of the bipyridine ligand, while those in the plane of the bipyridine remain close to linear. However, the crystal structure of PPN[Fe(phen)(CN-BPh3)4] does not display the same bowing effect (Ru-C-N = 176°), so there may be an electronic or crystal packing effect at play. Figure 7: IR spectrum of PPN2Ru(CF3bpy)(CN-BCF)4 with CN stretches highlighted in inset. 54 The C-N stretches in [Ru(CF3bpy)(CN-BCF)4]2- are shifted to much higher frequency (> 100 cm-1, Figure 7). This observation, which indicates that the C-N bond is strengthened by coordination of the borane, is also in line with the shifts observed in ferricyanide23 and other heteroleptic Ru complexes.26,29 Figure 8: UV-Vis spectra for PPN2Ru(CF3bpy)(CNBCF)4 in DCM (blue solid trace) and MeCN (orange broken trace). Addition of the boranes to [Ru(CF3bpy)(CN)4]2- induces a large blueshift in the optical absorption maximum, as the stronger Lewis acidity of BCF relative to water induces the cyanide ligands to become much better π acceptors. This strong ligand field lowers the energy of the Ru-d(π) orbitals, while minimally affecting the CF3bpy π orbitals, resulting in a blueshift in MeCN of the lowest-energy MLCT by nearly 8500 cm-1. The boronated complex displays solvatochromism (Figure 8), with a slightly redshifted and split MLCT in DCM, indicating there is still a dipole in the ground state. [Ru(CF3bpy)(CN-BCF)4]2- is also brightly emissive at 545 nm, with a long 55 excited-state lifetime of 3.4 µs and high quantum yield of 14.4%, and is photostable for weeks in solution under room lights. Figure 9: Cyclic voltammagram of 2.3 mM PPN2 Ru(CF3bpy)(CN-BCF)4 in 0.2 M Bu4NPF6-supported acetonitrile. Working electrode: glassy carbon. Counter electrode: Pt wire. Electrochemically, boronation with BCF induces a large anodic shift of 1.58 V in the potential of the Ru2+/3+ couple along with a 390 mV anodic shift of the CF3bpy0/·- couple (Figure 9), comparable to the shifts observed for the parent bpy complex.26,29 While the peak current ratio for the CF3bpy0/·- remains near-unity, the peak-to-peak separation increases with increasing scan rate, indicating that the electron transfer is reversible but slow on the timescale of the scan rates used. The heterogeneous chargetransfer rate constant (k0) determined by Nicholson analysis (see Figure S5) of the appropriate variable scan rate data is 0.009 cm s-1. The peak current ratios for the 56 Ru2+/3+ couple deviate significantly from unity (average for all scan rates measured = 0.79) and decreases as the scan rate decreases, indicating a loss of reversibility attributable to an EC mechanism. Because the Ru2+/3+ couple occurs very near the edge of the stability window for Bu4NPF6-supported MeCN, it is impossible to determine whether this electrochemical irreversibility is inherent to PPN2 Ru(CF3bpy)(CN-BCF)4 or a result of solvent or supporting electrolyte decomposition. Figure 10: Top: room temperature absorption and emission data for [Ru(CF3bpy)(CN-BCF)4]2- in acetonitrile. Bottom: Modified Latimer diagram with potentials given in V vs. Fc+/0. 57 Combining the electrochemical and photophysical data, a modified Latimer diagram can be constructed (Figure 10) to estimate the excited-state redox potentials for [Ru(CF3bpy)(CN-BCF)4]2-. [Ru(CF3bpy)(CN-BCF)4]2- is expected to be a strong excited-state oxidant and modest excited state reductant, with an excited state oxidation potential comparable to [Ru(bpz)3]2+.34 Conclusion A new member of the [Ru(diimine)(CN)4]2- has been synthesized using the CF3bpy ligand, and it displays spectroscopic properties expected for an electron-withdrawing diimine. Notably, the library of [Ru(diimine)(CN)4]2- complexes with electronwithdrawing diimine ligands is currently limited to bis(diazines) and HOOCbpy. [Ru(CF3bpy)(CN)4]2- represents an addition to this library that is nonreactive to protons, which may be desirable for certain applications. The borane adduct [Ru(CF3bpy)(CN-BCF)4]2- has also been synthesized, and it represents an important step toward high voltage symmetric redox flow battery electrolytes with a voltage difference of 3.2 V. While the Ru2+/3+ couple occurs too close to the edge of the solvent stability window to be useful as a flow battery electrolyte, the enhanced stability of the CF3bpy0/- couple indicates that a different isocyanoborato complex of CF3bpy such as Ru(CF3bpy)2(CN-BCF)2 might be able to achieve the right balance of properties. [Ru(CF3bpy)(CN-BCF)4]2- also has luminescence properties that suggest it may be a useful photoredox catalyst. With 1 V of oxidizing power vs. Fc+/0, it may be a competent catalyst for photooxidations that currently utilize [Ru(bpz)3]2+ or [Ir[dF(CF3)ppy]2(dtbbpy)]+ as catalysts. 58 References (1) Bignozzi, C. A.; Chiorboli, C.; Indelli, M. T.; Rampi Scandola, M. A.; Varani, G.; Scandola, F. Simple Poly(Pyridine)Ruthenium(II) Photosensitizer: (2,2’Bipyridine)Tetracyanoruthenate(II). J. Am. Chem. Soc. 1986, 108 (24), 7872–7873. https://doi.org/10.1021/ja00284a084. (2) Timpson, C. J.; Bignozzi, C. A.; Sullivan, B. P.; Kober, E. M.; Meyer, T. J. 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Electronic Structures and Photophysics of [M(Diimine)(CN-BR3)4]2- (M = Fe, Ru) Complexes. Manuscript in Preparation. (27) McNicholas, B.; Winkler, J. R.; Gray, H. B. Electronic Structure of Boronated, Group VIII Hexacyanometalates and Their Utility in Non-Aqueous Redox Flow Batteries and Cold Climate Energy Storage. Manuscript in preparation. (28) Nie, C.; McNicholas, B. J.; Gray, H. B.; Grubbs, R. H. Manuscript In Preparation. (29) Ngo, D. X. High Voltage Fe(II) and Ru(II) Symmetric Redox Flow Battery Electrolytes. Senior Thesis, California Institute of Technology, Pasadena, CA, 2019. 62 (30) Jiwan, J. L. H.; Wegewijs, B.; Indelli, M. T.; Scandola, F.; Braslavsky, S. E. Volume Changes Associated with Intramolecular Electron Transfer during MLCT State Formation. Time-Resolved Optoacoustic Studies of Ruthenium Cyano Complexes. Recl. Trav. Chim. Pays-Bas-J. R. Neth. Chem. Soc. 1995, 114 (11–12), 542-. (31) Indelli, M. T.; Ghirotti, M.; Prodi, A.; Chiorboli, C.; Scandola, F.; McClenaghan, N. D.; Puntoriero, F.; Campagna, S. Solvent Switching of Intramolecular Energy Transfer in Bichromophoric Systems: Photophysics of (2,2‘- Bipyridine)Tetracyanoruthenate(II)/Pyrenyl Complexes. Inorg. Chem. 2003, 42 (18), 5489–5497. https://doi.org/10.1021/ic034185x. (32) Garcia Posse, M. E.; Katz, N. E.; Baraldo, L. M.; Polonuer, D. D.; Colombano, C. G.; Olabe, J. A. Comparative Bonding and Photophysical Properties of 2,2’-Bipyridine and 2,2’-Bipyrazine in Tetracyano Complexes Containing Ruthenium and Osmium. Inorg. Chem. 1995, 34 (7), 1830–1835. https://doi.org/10.1021/ic00111a034. (33) Roffia, S.; Ciano, M. Electrochemical Behaviour of Dicyanobis(2,2′-Bipyridine) Ruthenium(II) and Dicyanobis(1,10-Phenanthroline) Ruthenium(II) Complexes. J. Electroanal. Chem. Interfacial Electrochem. 1977, 77 (3), 349–359. https://doi.org/10.1016/S0022-0728(77)80280-5. (34) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis. Chem. Rev. 2013, 113 (7), 5322–5363. https://doi.org/10.1021/cr300503r. (35) Krause, R. A.; Hexacyanoruthenate(II). Violette, C. Inorganica An Improved Chim. Acta Synthesis 1986, 113 of Potassium (2), 161–162. https://doi.org/10.1016/S0020-1693(00)82239-2. (36) Bard, A. J.; Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications, 2nd ed.; John Wiley & Sons: Hoboken, NJ, 2001. 63 (37) Nicholson, R. S. Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics. Anal. Chem. 1965, 37 (11), 1351–1355. https://doi.org/10.1021/ac60230a016. (38) Lavagnini, I.; Antiochia, R.; Magno, F. An Extended Method for the Practical Evaluation of the Standard Rate Constant from Cyclic Voltammetric Data. Electroanalysis 2004, 16 (6), 505–506. https://doi.org/10.1002/elan.200302851. (39) Sattler, W.; Ener, M. E.; Blakemore, J. D.; Rachford, A. A.; LaBeaume, P. J.; Thackeray, J. W.; Cameron, J. F.; Winkler, J. R.; Gray, H. B. Generation of Powerful Tungsten Reductants by Visible Light Excitation. J. Am. Chem. Soc. 2013, 135 (29), 10614–10617. https://doi.org/10.1021/ja4047119. (40) Suzuki, K.; Kobayashi, A.; Kaneko, S.; Takehira, K.; Yoshihara, T.; Ishida, H.; Shiina, Y.; Oishi, S.; Tobita, S. Reevaluation of Absolute Luminescence Quantum Yields of Standard Solutions Using a Spectrometer with an Integrating Sphere and a BackThinned CCD Detector. Phys. Chem. Chem. Phys. 2009, 11 (42), 9850–9860. https://doi.org/10.1039/B912178A. (41) Crosby, G. A.; Demas, J. N. Measurement of Photoluminescence Quantum Yields. Review. J. Phys. Chem. 1971, 75 (8), 991–1024. https://doi.org/10.1021/j100678a001. 64 Methods General Considerations Potassium hexacyanoruthenate(II) was synthesized by a known procedure35. 4,4’trifluoromethyl-2,2’-bipyridine (CF3bpy, Strem), bis(triphenylphosphine)iminium chloride (PPNCl, Millipore Sigma), and tris(pentafluorophenyl)borane (BCF, TCI) were used as received. NMR spectra were collected on a Varian 400 MHz spectrometer (δ in ppm, m: multiplet, s: singlet, d: doublet, t: triplet). UV-visible spectra were collected on a Cary 50 Bio or Cary 500 spectrometer. Solid-state infrared spectra were collected on a Thermo Scientific Nicolet iS5 FT-IR spectrometer with an iD5 ATR diamond. Synthesis & Characterization PPN2Ru(CF3bpy)(CN)4 K2Ru(CF3bpy)(CN)4 was synthesized with a modified version of the procedure published by Jiwan.30 To a boiling solution of K4Ru(CN)6 (400 mg, .908 mmol) and bpy (305 mg, 1.04 mmol) in 50 mL 1:1 methanol:water was added 400 μL 3.6 N CF3 H2SO4 (pH 4). The solution was refluxed for 24 h, over which time it slowly turned red, then cooled to room temperature and neutralized. Excess CF3bpy was removed by filtration and the solvent was removed. The remaining residue was purified by gel-filtration chromatography on a Sephadex G-15 column. Elution with water gave a main orange band free of excess K4Ru(CN)6. The main fraction was dried under vacuum to give K2Ru(CF3bpy)(CN)4, yield 30%. The cation was exchanged by precipitation from concentrated aqueous solution with a saturated solution of PPNCl (307 mg, .535 mmol in 20 mL water). The resulting brick-red precipitate was collected by filtration and dried in a desiccator or under vacuum until it turned green, yield 326 mg (25%). Single crystals suitable for X-ray diffraction analysis were grown by slow evaporation from DCM solution. 1H NMR (400 MHz, CD2Cl2): δ 65 10.02 (d, J = 8 Hz, 2H, 6,6’-H), 8.12 (s, 2H, 3,3’-H), 7.69-7.65 (m, 24H, PPN), 7.527.44 (m, 36H, PPN), 7.40 (d, J = 8 Hz, 2H, 5,5’-H). 19F NMR (CD2Cl2): δ -64.71. IR (cm-1, CN stretches) 2062, 2090. Anal. Calcd for C88H66F6N8P4Ru: C, 67.13; H, 4.23; N, 7.12. Found: C, 64.21; H, 4.28; N, 5.55. PPN2Ru(CF3bpy)(CN-BCF)4 In a nitrogen-filled glovebox, PPN2Ru(CF3bpy)(CN)4 (100 mg, 0.0637 mmol) and excess BCF (133 mg, 0.261 mmol) were each dissolved in minimal DCM. The two solutions were combined, causing a rapid color change from green to red to yellow. The solution was stirred for 1 h, then dried under vacuum. The resulting luminescent yellow solid was washed 3 x 10 mL hexanes, then dried thoroughly under vacuum. The resulting air-stable material was then further purified by flash chromatography on silica gel (eluent gradient from 100% hexanes to 90% dichloromethane in hexanes), affording 131 mg yellow product (0.0362 mmol, 56% yield). Single crystals suitable for X-ray diffraction analysis were grown from a saturated ethanol solution at –25°C. 1H NMR (400 MHz, CD2Cl2): δ 9.22 (d, J = 4 Hz, 2H, 6,6’-H), 8.29 (s, 2H, 3,3’-H), 7.65-7.59 (m, 14H, PPN + 5,5’-H), 7.51-7.40 (m, 48H, PPN). F NMR (CD2Cl2): δ -65.48 (s, 6F, CF3), -134.54 (dd, 12F, o-F), -135.00 (dd, 12F, 19 o-F), -161.57 (t, 6F, p-F), -162.03 (t, 6F, p-F), -167.01 (td, 12F, m-F), -167.29 (td, 12F, m-F). 11B NMR (CD2Cl2): δ -14.09. IR (cm-1, CN stretches) 2171, 2216. Anal. Calcd for C160H66F66N8P4Ru: C, 53.05; H, 1.84; N, 3.09. Found: C, 51.69; H, 2.09; N, 2.76. Electrochemical Measurements Cyclic voltammagrams were taken in a nitrogen-filled glovebox with a Gamry Reference 600 potentiostat in a standard 3-electrode cell containing a 3 mm diameter glassy carbon working electrode, a 0.01 M Ag+/0 in 0.1 M TBAPF6/MeCN quasireference electrode, and a platinum wire counter electrode and compensated for 85% of the measured uncompensated resistance (Ru) value. 66 Diffusion coefficients were calculated from linear fits of plots of the peak current versus the square root of the scan rate using the Randles-Sevcik equation (Equation S1),36 where ip (A) is the peak current, n is the number of electrons transferred (1), F (C mol-1) is the Faraday constant, C (mol cm-1) is the bulk concentration of analyte, ν (V s-1) is the scan rate, DO (cm2 s-1) is the diffusion coefficient of the oxidized analyte, R (J mol-1 K-1) is the ideal gas constant, and T (K) is the temperature. 𝑖𝑖𝑝𝑝 = 0.446𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 � 𝑛𝑛𝑛𝑛𝑛𝑛𝐷𝐷𝑂𝑂 1/2 � (S1) 𝑅𝑅𝑅𝑅 The heterogeneous electron transfer rate constant (k0) for the CF3bpy0/·- couple of PPN2Ru(CF3bpy)(CN -BCF)4 was determined using Nicholson’s kinetic parameter Ψ37 along with Lavagnini’s numerical interpretation of Ψ38 (Equations S2 and S3). 𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 −1/2 � (S2) Ψ = 𝑘𝑘0 � 𝑅𝑅𝑅𝑅 Ψ= −.06288 + .0021𝜒𝜒 (S3) 1 − 0.017𝜒𝜒 χ (mV) is the peak-to-peak separation. For sufficiently fast scan rates with respect to the electron transfer (i.e. in the region where χ is observed to vary with scan rate, where Ψ becomes small), plots of Ψ vs. ν-1/2 become linear, and k0 may be calculated from the slope. For the other electrochemical couples observed, χ did not vary with the scan rates used, and would have required very high (> 3 V/s) scan rates for this analysis. Photophysical Measurements Steady-state and time-resolved spectroscopic measurements were carried out in the Beckman Institute Laser Resource Center (California Institute of Technology) using methods described previously.39 67 Quantum yields (φPL) were measured by comparison of deaerated, optically dilute solutions of the molecule of interest to [Ru(bpy)3](PF6)2 in aerated and deaerated MeCN (φPL = 0.018 for aerated solutions and 0.095 for aerated solutions40) according to Equation S4.41 𝐴𝐴 𝜑𝜑 = 𝜑𝜑𝑟𝑟𝑟𝑟𝑟𝑟 𝑟𝑟𝑟𝑟𝑟𝑟 𝐴𝐴 𝐼𝐼 𝐼𝐼 𝜂𝜂 2 𝑟𝑟𝑟𝑟𝑟𝑟 𝜂𝜂𝑟𝑟𝑟𝑟𝑟𝑟 2 (S4) Subscript “ref” refers to the reference solutions, A are the absorbances at the exciting wavelength (450 nm for all measurements), I are the integrated emission intensities, and η are the refractive indices of the solvents used. Absorption measurements were taken before and after emission spectra to ensure there was no photodecomposition. Emission spectra were taken twice with different integration times to ensure there were no significant differences. The resulting luminescence decay traces were fitted as an exponential decay to determine the excited state lifetimes (τ). 68 Supporting Data Figure S1: Randles-Sevcik plot for PPN2Ru(CF3bpy)(CN)4; D = 5.7 x 10-6 cm2 s-1. Figure S2: Variable scan rate cyclic voltammagrams for PPN2Ru(CF3bpy)(CN)4. 33 mM PPN2 Ru(CF3bpy)(CN)4 in 0.2 M Bu4NPF6-supported acetonitrile. Working electrode: glassy carbon. Counter electrode: Pt wire. 69 Figure S3: Randles-Sevcik plot for PPN2Ru(CF3bpy)(CN-BCF)4; D = 7.4 x 10-6 cm2 s-1 (top), 2.4 x 10-6 cm2 s-1 (bottom). Figure S4: Variable scan rate cyclic voltammetry of PPN2Ru(CF3bpy)(CN-BCF)4. . 2.3 mM PPN2 Ru(CF3bpy)(CN-BCF)4 in 0.2 M Bu4NPF6-supported acetonitrile. Working electrode: glassy carbon. Counter electrode: Pt wire. 70 0.8 0.7 y = 9.167E-03x - 7.070E-02 R² = 9.832E-01 0.6 Ψ 0.5 0.4 0.3 0.2 0.1 0 0 10 20 30 40 50 60 70 (DnFνπ/RT)-1/2 Figure S5: Nicholson analysis of the CF3bpy0/·- couple of PPN2Ru(CF3bpy)(CN-BCF)4, with a slope of k0. Figure S6: Steady-state emission spectrum of aqueous K2Ru(CF3bpy)(CN)4 excited at 400 nm. 80 90 71 Table S1: Measurement of quantum yield PPN2Ru(CF3bpy)(CN-BCF)4. for Sample A450 I φref φsample wrt Aerated 0.0747 8.30 x105 0.018 0.132 0.1043 5.08 x106 0.095 0.159 Sample 1 0.0467 3.79 x106 - - Aerated 0.0743 1.10 x106 0.018 0.131 0.0961 6.43 x106 0.095 0.153 0.0464 5.00 x106 - - [Ru(bpy)3]2+ 1 Deaerated [Ru(bpy)3]2+ 1 [Ru(bpy)3]2+ 2 Deaerated [Ru(bpy)3]2+ 2 Sample 2 0.144 average Figure S7: Left, time-resolved luminescence data for PPN2Ru(CF3bpy)(CN-BCF)4. Right, linear fit to determine lifetime. The slope of the fit is the inverse of τ = 3.44 µs. 72 Figure S8: Dilution series for molar absorptivity of [Ru(CF3bpy)(CN)4]2- (K salt in water, PPN salt in MeCN) and linear fits. All measurements in 5 mm cuvette. Extinction coefficients are ε332 = 3660 M-1cm-1, ε443 = 3170 M-1cm-1 in water and ε414 = 6190 M-1cm-1, ε589 = 3770 M-1cm-1 in MeCN. 73 Figure S9: Dilution series for molar absorptivity of All PPN2Ru(CF3bpy)(CN-BCF)4 and linear fits. measurements in 5 mm cuvette. Extinction coefficients are ε315 = 1460 M-1cm-1, ε395 = 958 M-1cm-1, ε410 = 1020 M-1cm-1 in DCM and ε320 = 3860 M-1cm-1, ε393 = 4440 M1cm-1 in MeCN. 74 19F Figure S10: NMR PPN2Ru(CF3bpy)(CN)4 in CD2Cl2. spectrum of 75 1H Figure S11: NMR spectrum of PPN2Ru(CF3bpy)(CN)4 in CD2Cl2. Peaks upfield of 3 ppm are attributable to water, trace solvents, and silicone grease. 76 Figure S12: 11B NMR spectrum of PPN2Ru(CF3bpy)(CNBCF)4 in CD2Cl2 acquired in a quartz NMR tube. 77 Figure S13: 19F NMR spectrum of PPN2Ru(CF3bpy)(CNBCF)4 in CD2Cl2 with insets showing detail of BCF peaks. 78 Figure S14: 1H NMR spectrum of PPN2Ru(CF3bpy)(CNBCF)4 in CD2Cl2. Peaks upfield of 2 ppm are attributable to water, pentane, and silicone grease. 79 APPENDIX Crystal Data PPN2Ru(CF3bpy)(CN)4 Table 1. Crystal data and structure refinement for v19188. Identification code v19188 Empirical formula C90.22 H70.45 Cl4.45 F6 N8 P4 Ru Formula weight 1763.39 Temperature 100.01 K Wavelength 1.54178 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 14.4682(16) Å α= 104.716(5)° b = 14.6308(17) Å β= 101.091(4)° c = 21.319(2) Å γ = 105.092(6)° Volume 4049.6(8) Å3 Z 2 Density (calculated) 1.446 g/cm3 Absorption coefficient 4.214 mm-1 F(000) 1803 Crystal size 0.26 x 0.23 x 0.07 mm3 Theta range for data collection 3.292 to 79.375°. Index ranges -18 ≤ h ≤ 18, -18 ≤ k ≤ 18, -27 ≤ l ≤ 25 Reflections collected 196069 80 Independent reflections 16794 [R(int) = 0.0435] Completeness to theta = 67.679° 99.6 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.0000 and 0.6998 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 16794 / 3 / 1075 Goodness-of-fit on F2 1.081 Final R indices [I>2sigma(I)] R1 = 0.0339, wR2 = 0.0783 R indices (all data) R1 = 0.0373, wR2 = 0.0817 Extinction coefficient n/a Largest diff. peak and hole 0.743 and -0.937 e.Å-3 81 Table 2. Atomic coordinates ( x 105), equivalent isotropic displacement parameters (Å2x 104), and population for v19188. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ____________________________________________________________________________________ x y z U(eq) pop ____________________________________________________________________________________ Ru(1) 45462(2) 32209(2) 32147(2) 164(1) 1 F(1) 91407(11) 61245(17) 52808(9) 662(6) 1 F(2) 86565(14) 73757(13) 53059(9) 714(6) 1 F(3) 83829(9) 66006(11) 60068(6) 394(3) 1 F(4) 47136(12) 19524(12) 61075(8) 445(4) 1 F(5) 50334(11) 35255(11) 65956(6) 426(4) 1 F(6) 35186(10) 25435(10) 61844(7) 336(3) 1 N(1) 57172(11) 44418(11) 39063(8) 168(3) 1 N(2) 44080(11) 30596(11) 41383(8) 178(3) 1 N(3) 28847(12) 11226(13) 24313(9) 259(4) 1 N(4) 50189(13) 38045(12) 19468(8) 242(4) 1 N(5) 61750(12) 20869(13) 32206(8) 236(3) 1 N(6) 29843(13) 44400(13) 32600(9) 244(4) 1 C(1) 63788(14) 51207(14) 37447(9) 199(4) 1 C(2) 72338(14) 58029(14) 42083(10) 213(4) 1 C(3) 74264(14) 57990(14) 48720(10) 213(4) 1 C(4) 67457(14) 51358(14) 50573(9) 189(4) 1 C(5) 58956(13) 44635(13) 45605(9) 166(3) 1 C(6) 51363(13) 37123(13) 46959(9) 174(4) 1 82 C(7) 51563(14) 36511(14) 53405(9) 185(4) 1 C(8) 44035(15) 29050(14) 54083(10) 214(4) 1 C(9) 36391(16) 22605(15) 48432(11) 260(4) 1 C(10) 36642(15) 23631(15) 42220(10) 239(4) 1 C(11) 83926(16) 64723(17) 53739(11) 309(5) 1 C(12) 44228(16) 27452(16) 60747(11) 269(4) 1 C(13) 34720(14) 19137(14) 26794(9) 202(4) 1 C(14) 48137(14) 35513(14) 23903(10) 208(4) 1 C(15) 55656(14) 24668(13) 31992(9) 184(4) 1 C(16) 35352(14) 39885(14) 32245(9) 197(4) 1 P(1) 67865(3) 90701(3) 20102(2) 169(1) 1 P(2) 77912(3) 101220(3) 11525(2) 175(1) 1 N(7) 75261(12) 94480(13) 16056(8) 228(3) 1 C(17) 55407(14) 91013(15) 17491(9) 201(4) 1 C(18) 53712(15) 100132(15) 19613(10) 237(4) 1 C(19) 44377(16) 100897(18) 17289(12) 303(5) 1 C(20) 36646(17) 92440(20) 13041(12) 361(5) 1 C(21) 38197(17) 83308(19) 11108(12) 359(5) 1 C(22) 47588(16) 82526(16) 13196(10) 276(4) 1 C(23) 66956(14) 77873(14) 19183(10) 208(4) 1 C(24) 60693(15) 72262(15) 22065(10) 233(4) 1 C(25) 60154(17) 62415(15) 21326(11) 284(4) 1 C(26) 65817(19) 58103(17) 17746(13) 353(5) 1 C(27) 71980(20) 63572(18) 14792(14) 394(6) 1 83 C(28) 72561(17) 73473(16) 15512(12) 296(5) 1 C(29) 72746(14) 97990(14) 28941(9) 192(4) 1 C(30) 82215(15) 105111(15) 31265(11) 251(4) 1 C(31) 86106(17) 110626(16) 38089(11) 315(5) 1 C(32) 80624(18) 109060(16) 42574(11) 321(5) 1 C(33) 71165(17) 102017(16) 40276(10) 292(5) 1 C(34) 67182(15) 96472(15) 33479(10) 235(4) 1 C(35) 70075(14) 108762(14) 10521(10) 199(4) 1 C(36) 70200(15) 116017(15) 16302(10) 247(4) 1 C(37) 63708(16) 121439(15) 15971(11) 269(4) 1 C(38) 57064(15) 119760(16) 9814(12) 279(4) 1 C(39) 57018(15) 112781(16) 4037(11) 277(4) 1 C(40) 63519(14) 107199(15) 4344(10) 232(4) 1 C(41) 76969(14) 93400(14) 3260(9) 207(4) 1 C(42) 69772(15) 83920(15) 646(10) 247(4) 1 C(43) 68344(16) 77949(16) -5916(11) 285(4) 1 C(44) 74020(20) 81416(18) -9842(11) 363(5) 1 C(45) 81160(20) 90760(20) -7270(13) 489(7) 1 C(46) 82759(19) 96768(17) -694(12) 366(5) 1 C(47) 90511(14) 109529(14) 15232(9) 198(4) 1 C(48) 93517(16) 118815(16) 14293(11) 281(4) 1 C(49) 103328(17) 125099(17) 17265(13) 337(5) 1 C(50) 110072(16) 122226(18) 21161(12) 347(5) 1 C(51) 107113(16) 112940(20) 22057(12) 353(5) 1 84 C(52) 97386(15) 106593(17) 19113(11) 278(4) 1 P(3) 5024(4) 62485(4) 31836(3) 228(1) 1 P(4) 7117(4) 59281(4) 17572(3) 221(1) 1 N(8) 8696(13) 62742(13) 25386(9) 277(4) 1 C(53) 15586(14) 66411(14) 39049(10) 213(4) 1 C(54) 14760(16) 63649(15) 44762(11) 248(4) 1 C(55) 22676(17) 67842(15) 50596(11) 269(4) 1 C(56) 31393(16) 74778(15) 50705(11) 270(4) 1 C(57) 32294(16) 77394(16) 45001(11) 273(4) 1 C(58) 24430(15) 73253(15) 39145(10) 234(4) 1 C(59) -1517(15) 71356(16) 33663(13) 299(5) 1 C(60) -3310(20) 74200(20) 39906(17) 495(7) 1 C(61) -8110(30) 81230(30) 41331(19) 620(10) 1 C(62) -11110(20) 85410(20) 36526(17) 483(7) 1 C(63) -9290(20) 82734(19) 30348(14) 443(6) 1 C(64) -4566(19) 75661(18) 28864(13) 388(6) 1 C(65) -2896(15) 50589(15) 31583(11) 247(4) 1 C(66) 1051(15) 42825(15) 31416(10) 249(4) 1 C(67) -4823(15) 33724(15) 31590(10) 256(4) 1 C(68) -14518(16) 32423(15) 31985(10) 262(4) 1 C(69) -18540(16) 40023(16) 31940(12) 309(5) 1 C(70) -12780(16) 49134(17) 31732(12) 311(5) 1 C(71) 17784(15) 56443(15) 15653(11) 260(4) 1 C(72) 20038(17) 57017(18) 9657(12) 324(5) 1 85 C(73) 27827(19) 54020(20) 7984(14) 411(6) 1 C(74) 33374(19) 50430(20) 12255(15) 433(6) 1 C(75) 31230(18) 49950(20) 18234(14) 395(6) 1 C(76) 23418(16) 52916(17) 19975(12) 321(5) 1 C(77) 5281(15) 68979(15) 14077(10) 231(4) 1 C(78) 12210(16) 78624(16) 17059(11) 269(4) 1 C(79) 10753(17) 86447(16) 14833(11) 291(4) 1 C(80) 2425(17) 84625(16) 9620(12) 304(5) 1 C(81) -4425(17) 75050(17) 6580(11) 301(5) 1 C(82) -3030(15) 67216(16) 8805(11) 257(4) 1 C(83) -3668(15) 48408(15) 12968(10) 237(4) 1 C(84) -3522(16) 40972(15) 7443(11) 268(4) 1 C(85) -12164(17) 32928(16) 3838(11) 307(5) 1 C(86) -20858(17) 32331(16) 5780(12) 311(5) 1 C(87) -21012(16) 39672(16) 11287(12) 310(5) 1 C(88) -12468(15) 47742(15) 14870(11) 276(4) 1 Cl(1) 38869(4) 87792(4) 28961(3) 302(2) 0.93(1) Cl(2) 45630(5) 102685(5) 42351(3) 402(2) 0.93(1) C(89) 43369(18) 100770(18) 33600(12) 300(5) 0.93(1) Cl(3) 50678(16) 56800(15) 735(13) 805(6) 0.5 Cl(4) 53814(14) 38163(16) 1177(14) 874(6) 0.5 C(90) 47140(90) 45930(110) 2630(70) 2800(180) 0.5 Cl(5) 11699(9) 102985(9) 45590(6) 371(4) 0.46(1) Cl(6) 17995(13) 98342(14) 33269(8) 340(4) 0.46(1) 86 C(91) 16830(50) 95430(40) 40720(30) 299(11) 0.46(1) Cl(7) 9270(14) 107714(14) 37162(10) 431(6) 0.33(1) Cl(8) 20340(16) 94144(16) 38323(15) 508(7) 0.33(1) C(92) 13900(80) 98950(70) 32840(50) 300(20) 0.33(1) ____________________________________________________________________________________ 87 Table 3. Bond lengths [Å] and angles [°] for v19188. _____________________________________________________ Ru(1)-N(1) 2.0881(15) Ru(1)-N(2) 2.0822(16) Ru(1)-C(13) 2.0091(19) Ru(1)-C(14) 2.017(2) Ru(1)-C(15) 2.060(2) Ru(1)-C(16) 2.063(2) F(1)-C(11) 1.337(3) F(2)-C(11) 1.330(3) F(3)-C(11) 1.318(3) F(4)-C(12) 1.346(3) F(5)-C(12) 1.330(3) F(6)-C(12) 1.343(2) N(1)-C(1) 1.352(2) N(1)-C(5) 1.359(2) N(2)-C(6) 1.361(2) N(2)-C(10) 1.350(2) N(3)-C(13) 1.160(3) N(4)-C(14) 1.161(3) N(5)-C(15) 1.158(3) N(6)-C(16) 1.162(3) C(1)-C(2) 1.374(3) C(2)-C(3) 1.390(3) 88 C(3)-C(4) 1.384(3) C(3)-C(11) 1.497(3) C(4)-C(5) 1.393(3) C(5)-C(6) 1.467(2) C(6)-C(7) 1.395(3) C(7)-C(8) 1.386(3) C(8)-C(9) 1.390(3) C(8)-C(12) 1.494(3) C(9)-C(10) 1.376(3) P(1)-N(7) 1.5761(16) P(1)-C(17) 1.797(2) P(1)-C(23) 1.804(2) P(1)-C(29) 1.8062(19) P(2)-N(7) 1.5753(17) P(2)-C(35) 1.797(2) P(2)-C(41) 1.798(2) P(2)-C(47) 1.7969(19) C(17)-C(18) 1.397(3) C(17)-C(22) 1.397(3) C(18)-C(19) 1.390(3) C(19)-C(20) 1.387(3) C(20)-C(21) 1.384(4) C(21)-C(22) 1.390(3) C(23)-C(24) 1.398(3) 89 C(23)-C(28) 1.395(3) C(24)-C(25) 1.389(3) C(25)-C(26) 1.385(3) C(26)-C(27) 1.390(3) C(27)-C(28) 1.396(3) C(29)-C(30) 1.393(3) C(29)-C(34) 1.396(3) C(30)-C(31) 1.392(3) C(31)-C(32) 1.380(4) C(32)-C(33) 1.388(3) C(33)-C(34) 1.389(3) C(35)-C(36) 1.401(3) C(35)-C(40) 1.393(3) C(36)-C(37) 1.381(3) C(37)-C(38) 1.391(3) C(38)-C(39) 1.384(3) C(39)-C(40) 1.400(3) C(41)-C(42) 1.397(3) C(41)-C(46) 1.387(3) C(42)-C(43) 1.392(3) C(43)-C(44) 1.377(3) C(44)-C(45) 1.379(4) C(45)-C(46) 1.391(3) C(47)-C(48) 1.392(3) 90 C(47)-C(52) 1.395(3) C(48)-C(49) 1.393(3) C(49)-C(50) 1.378(4) C(50)-C(51) 1.388(4) C(51)-C(52) 1.386(3) P(3)-N(8) 1.5721(19) P(3)-C(53) 1.795(2) P(3)-C(59) 1.804(2) P(3)-C(65) 1.799(2) P(4)-N(8) 1.5648(19) P(4)-C(71) 1.792(2) P(4)-C(77) 1.815(2) P(4)-C(83) 1.804(2) C(53)-C(54) 1.394(3) C(53)-C(58) 1.397(3) C(54)-C(55) 1.391(3) C(55)-C(56) 1.390(3) C(56)-C(57) 1.383(3) C(57)-C(58) 1.389(3) C(59)-C(60) 1.385(4) C(59)-C(64) 1.392(3) C(60)-C(61) 1.388(4) C(61)-C(62) 1.378(4) C(62)-C(63) 1.372(4) 91 C(63)-C(64) 1.386(4) C(65)-C(66) 1.394(3) C(65)-C(70) 1.398(3) C(66)-C(67) 1.395(3) C(67)-C(68) 1.388(3) C(68)-C(69) 1.384(3) C(69)-C(70) 1.393(3) C(71)-C(72) 1.396(3) C(71)-C(76) 1.397(3) C(72)-C(73) 1.387(3) C(73)-C(74) 1.389(4) C(74)-C(75) 1.383(4) C(75)-C(76) 1.392(3) C(77)-C(78) 1.401(3) C(77)-C(82) 1.395(3) C(78)-C(79) 1.394(3) C(79)-C(80) 1.387(3) C(80)-C(81) 1.390(3) C(81)-C(82) 1.393(3) C(83)-C(84) 1.393(3) C(83)-C(88) 1.396(3) C(84)-C(85) 1.394(3) C(85)-C(86) 1.387(3) C(86)-C(87) 1.384(3) 92 C(87)-C(88) 1.387(3) Cl(1)-C(89) 1.778(2) Cl(2)-C(89) 1.766(3) Cl(3)-C(90) 1.713(15) Cl(4)-C(90) 1.682(15) Cl(5)-C(91) 1.729(6) Cl(6)-C(91) 1.774(5) Cl(7)-C(92) 1.740(10) Cl(8)-C(92) 1.753(10) N(2)-Ru(1)-N(1) 77.38(6) C(13)-Ru(1)-N(1) 169.04(7) C(13)-Ru(1)-N(2) 93.38(7) C(13)-Ru(1)-C(14) 94.05(8) C(13)-Ru(1)-C(15) 88.31(7) C(13)-Ru(1)-C(16) 92.10(7) C(14)-Ru(1)-N(1) 95.26(7) C(14)-Ru(1)-N(2) 172.56(7) C(14)-Ru(1)-C(15) 89.53(7) C(14)-Ru(1)-C(16) 89.81(7) C(15)-Ru(1)-N(1) 85.99(6) C(15)-Ru(1)-N(2) 91.02(7) C(15)-Ru(1)-C(16) 179.25(7) C(16)-Ru(1)-N(1) 93.71(7) 93 C(16)-Ru(1)-N(2) 89.59(7) C(1)-N(1)-Ru(1) 125.27(12) C(1)-N(1)-C(5) 118.10(16) C(5)-N(1)-Ru(1) 115.99(12) C(6)-N(2)-Ru(1) 116.38(12) C(10)-N(2)-Ru(1) 125.25(13) C(10)-N(2)-C(6) 118.37(16) N(1)-C(1)-C(2) 122.72(17) C(1)-C(2)-C(3) 118.78(18) C(2)-C(3)-C(11) 119.92(18) C(4)-C(3)-C(2) 119.78(17) C(4)-C(3)-C(11) 120.22(18) C(3)-C(4)-C(5) 118.33(17) N(1)-C(5)-C(4) 122.22(17) N(1)-C(5)-C(6) 114.74(16) C(4)-C(5)-C(6) 123.03(17) N(2)-C(6)-C(5) 114.71(16) N(2)-C(6)-C(7) 121.94(17) C(7)-C(6)-C(5) 123.34(17) C(8)-C(7)-C(6) 118.39(17) C(7)-C(8)-C(9) 119.79(18) C(7)-C(8)-C(12) 121.17(18) C(9)-C(8)-C(12) 118.96(18) C(10)-C(9)-C(8) 118.80(18) 94 N(2)-C(10)-C(9) 122.61(18) F(1)-C(11)-C(3) 111.25(19) F(2)-C(11)-F(1) 105.0(2) F(2)-C(11)-C(3) 111.78(18) F(3)-C(11)-F(1) 107.54(19) F(3)-C(11)-F(2) 107.0(2) F(3)-C(11)-C(3) 113.79(17) F(4)-C(12)-C(8) 111.10(17) F(5)-C(12)-F(4) 107.15(19) F(5)-C(12)-F(6) 106.95(17) F(5)-C(12)-C(8) 113.34(17) F(6)-C(12)-F(4) 105.46(16) F(6)-C(12)-C(8) 112.37(18) N(3)-C(13)-Ru(1) 172.28(18) N(4)-C(14)-Ru(1) 175.11(17) N(5)-C(15)-Ru(1) 176.21(16) N(6)-C(16)-Ru(1) 177.03(17) N(7)-P(1)-C(17) 116.71(9) N(7)-P(1)-C(23) 107.03(9) N(7)-P(1)-C(29) 110.15(9) C(17)-P(1)-C(23) 107.30(9) C(17)-P(1)-C(29) 106.52(9) C(23)-P(1)-C(29) 108.92(9) N(7)-P(2)-C(35) 114.43(9) 95 N(7)-P(2)-C(41) 109.29(9) N(7)-P(2)-C(47) 109.10(9) C(35)-P(2)-C(41) 107.79(9) C(35)-P(2)-C(47) 107.44(9) C(47)-P(2)-C(41) 108.65(9) P(2)-N(7)-P(1) 146.60(12) C(18)-C(17)-P(1) 118.40(15) C(18)-C(17)-C(22) 119.86(19) C(22)-C(17)-P(1) 121.69(16) C(19)-C(18)-C(17) 120.38(19) C(20)-C(19)-C(18) 119.4(2) C(21)-C(20)-C(19) 120.4(2) C(20)-C(21)-C(22) 120.7(2) C(21)-C(22)-C(17) 119.2(2) C(24)-C(23)-P(1) 121.08(15) C(28)-C(23)-P(1) 119.40(15) C(28)-C(23)-C(24) 119.52(18) C(25)-C(24)-C(23) 120.10(19) C(26)-C(25)-C(24) 120.3(2) C(25)-C(26)-C(27) 120.1(2) C(26)-C(27)-C(28) 119.9(2) C(23)-C(28)-C(27) 120.0(2) C(30)-C(29)-P(1) 119.61(15) C(30)-C(29)-C(34) 119.70(18) 96 C(34)-C(29)-P(1) 120.69(15) C(31)-C(30)-C(29) 120.0(2) C(32)-C(31)-C(30) 120.2(2) C(31)-C(32)-C(33) 120.0(2) C(32)-C(33)-C(34) 120.4(2) C(33)-C(34)-C(29) 119.71(19) C(36)-C(35)-P(2) 117.88(15) C(40)-C(35)-P(2) 122.39(15) C(40)-C(35)-C(36) 119.60(19) C(37)-C(36)-C(35) 120.69(19) C(36)-C(37)-C(38) 119.6(2) C(39)-C(38)-C(37) 120.3(2) C(38)-C(39)-C(40) 120.4(2) C(35)-C(40)-C(39) 119.37(19) C(42)-C(41)-P(2) 118.57(15) C(46)-C(41)-P(2) 121.74(16) C(46)-C(41)-C(42) 119.58(19) C(43)-C(42)-C(41) 120.14(19) C(44)-C(43)-C(42) 119.9(2) C(43)-C(44)-C(45) 120.2(2) C(44)-C(45)-C(46) 120.7(2) C(41)-C(46)-C(45) 119.6(2) C(48)-C(47)-P(2) 121.22(15) C(48)-C(47)-C(52) 119.56(18) 97 C(52)-C(47)-P(2) 119.21(15) C(47)-C(48)-C(49) 119.8(2) C(50)-C(49)-C(48) 120.5(2) C(49)-C(50)-C(51) 119.8(2) C(52)-C(51)-C(50) 120.3(2) C(51)-C(52)-C(47) 120.0(2) N(8)-P(3)-C(53) 109.52(9) N(8)-P(3)-C(59) 110.65(10) N(8)-P(3)-C(65) 116.31(10) C(53)-P(3)-C(59) 105.67(10) C(53)-P(3)-C(65) 106.69(9) C(65)-P(3)-C(59) 107.41(10) N(8)-P(4)-C(71) 110.15(10) N(8)-P(4)-C(77) 111.03(10) N(8)-P(4)-C(83) 114.13(10) C(71)-P(4)-C(77) 108.35(9) C(71)-P(4)-C(83) 107.57(10) C(83)-P(4)-C(77) 105.33(9) P(4)-N(8)-P(3) 151.97(12) C(54)-C(53)-P(3) 121.17(15) C(54)-C(53)-C(58) 120.01(19) C(58)-C(53)-P(3) 118.43(15) C(55)-C(54)-C(53) 119.96(19) C(56)-C(55)-C(54) 119.8(2) 98 C(57)-C(56)-C(55) 120.3(2) C(56)-C(57)-C(58) 120.3(2) C(57)-C(58)-C(53) 119.54(19) C(60)-C(59)-P(3) 120.69(18) C(60)-C(59)-C(64) 119.1(2) C(64)-C(59)-P(3) 120.18(19) C(59)-C(60)-C(61) 120.3(3) C(62)-C(61)-C(60) 120.0(3) C(63)-C(62)-C(61) 120.3(3) C(62)-C(63)-C(64) 120.1(2) C(63)-C(64)-C(59) 120.2(3) C(66)-C(65)-P(3) 118.89(16) C(66)-C(65)-C(70) 119.98(19) C(70)-C(65)-P(3) 121.11(16) C(65)-C(66)-C(67) 119.6(2) C(68)-C(67)-C(66) 120.2(2) C(69)-C(68)-C(67) 120.11(19) C(68)-C(69)-C(70) 120.3(2) C(69)-C(70)-C(65) 119.7(2) C(72)-C(71)-P(4) 120.56(16) C(72)-C(71)-C(76) 120.0(2) C(76)-C(71)-P(4) 119.30(17) C(73)-C(72)-C(71) 119.9(2) C(72)-C(73)-C(74) 120.2(2) 99 C(75)-C(74)-C(73) 120.1(2) C(74)-C(75)-C(76) 120.4(2) C(75)-C(76)-C(71) 119.5(2) C(78)-C(77)-P(4) 118.24(15) C(82)-C(77)-P(4) 122.04(15) C(82)-C(77)-C(78) 119.63(19) C(79)-C(78)-C(77) 120.2(2) C(80)-C(79)-C(78) 119.7(2) C(79)-C(80)-C(81) 120.5(2) C(80)-C(81)-C(82) 120.1(2) C(81)-C(82)-C(77) 119.90(19) C(84)-C(83)-P(4) 121.78(16) C(84)-C(83)-C(88) 119.76(19) C(88)-C(83)-P(4) 118.40(16) C(83)-C(84)-C(85) 119.9(2) C(86)-C(85)-C(84) 119.9(2) C(87)-C(86)-C(85) 120.4(2) C(86)-C(87)-C(88) 120.1(2) C(87)-C(88)-C(83) 120.0(2) Cl(2)-C(89)-Cl(1) 110.79(13) Cl(4)-C(90)-Cl(3) 117.3(8) Cl(5)-C(91)-Cl(6) 112.9(3) Cl(7)-C(92)-Cl(8) 111.4(5) _____________________________________________________________ 100 Symmetry transformations used to generate equivalent atoms: 101 Table 4. Anisotropic displacement parameters (Å2x 104) for v19188. The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ Ru(1) 173(1) 152(1) 135(1) 22(1) 39(1) 30(1) F(1) 200(7) 1136(16) 456(9) 49(10) 20(6) 155(8) F(2) 684(11) 496(10) 497(10) 294(8) -275(8) -378(9) F(3) 288(7) 517(8) 188(6) 81(6) -5(5) -96(6) F(4) 607(9) 523(9) 541(9) 412(8) 367(8) 345(8) F(5) 481(8) 472(8) 197(6) 126(6) 79(6) -60(7) F(6) 357(7) 422(7) 315(7) 188(6) 211(6) 112(6) N(1) 186(7) 156(7) 155(7) 29(6) 66(6) 52(6) N(2) 196(7) 155(7) 173(7) 32(6) 65(6) 50(6) N(3) 200(8) 214(8) 296(9) 11(7) 27(7) 59(7) N(4) 307(9) 216(8) 175(8) 48(7) 76(7) 48(7) N(5) 224(8) 243(8) 218(8) 61(7) 49(6) 58(7) N(6) 274(9) 240(8) 221(8) 67(7) 72(7) 92(7) C(1) 232(9) 207(9) 152(8) 50(7) 74(7) 55(8) C(2) 211(9) 210(9) 203(9) 77(7) 77(7) 21(8) C(3) 187(9) 214(9) 203(9) 54(7) 31(7) 38(8) C(4) 200(9) 200(9) 165(9) 62(7) 49(7) 57(7) C(5) 181(8) 172(8) 156(8) 45(7) 64(7) 68(7) C(6) 180(8) 166(8) 183(9) 43(7) 67(7) 68(7) 102 C(7) 197(9) 181(9) 184(9) 53(7) 66(7) 67(7) C(8) 262(10) 205(9) 213(9) 84(8) 119(8) 82(8) C(9) 280(10) 193(9) 287(11) 71(8) 136(8) 11(8) C(10) 242(10) 190(9) 233(10) 32(8) 73(8) 13(8) C(11) 240(10) 366(12) 238(10) 131(9) 29(8) -40(9) C(12) 319(11) 269(10) 269(10) 140(9) 137(9) 85(9) C(13) 190(9) 228(9) 186(9) 42(7) 49(7) 88(8) C(14) 185(9) 164(8) 206(9) -13(7) 12(7) 44(7) C(15) 194(9) 151(8) 134(8) 12(7) 32(7) -18(7) C(16) 229(9) 171(8) 139(8) 29(7) 47(7) 4(8) P(1) 189(2) 149(2) 158(2) 47(2) 63(2) 29(2) P(2) 176(2) 175(2) 154(2) 53(2) 54(2) 20(2) N(7) 243(8) 241(8) 235(8) 113(7) 110(7) 71(7) C(17) 211(9) 233(9) 157(8) 71(7) 64(7) 52(8) C(18) 232(9) 249(10) 242(10) 86(8) 114(8) 58(8) C(19) 295(11) 395(12) 322(11) 169(10) 162(9) 170(10) C(20) 231(10) 547(15) 356(12) 215(11) 89(9) 134(10) C(21) 262(11) 411(13) 278(11) 99(10) -31(9) -8(10) C(22) 295(11) 261(10) 204(10) 54(8) 17(8) 36(9) C(23) 246(9) 170(9) 192(9) 46(7) 68(7) 48(7) C(24) 306(10) 200(9) 200(9) 62(7) 111(8) 65(8) C(25) 371(12) 195(9) 281(11) 90(8) 125(9) 45(9) C(26) 469(14) 203(10) 427(13) 106(9) 186(11) 126(10) C(27) 504(14) 268(11) 521(15) 132(11) 306(12) 183(11) 103 C(28) 343(11) 241(10) 350(12) 105(9) 191(9) 90(9) C(29) 240(9) 150(8) 176(9) 49(7) 41(7) 59(7) C(30) 261(10) 204(9) 255(10) 97(8) 35(8) 23(8) C(31) 337(11) 189(9) 305(11) 56(8) -48(9) 23(9) C(32) 468(13) 227(10) 202(10) 2(8) -18(9) 152(10) C(33) 411(12) 293(11) 189(10) 46(8) 87(9) 168(10) C(34) 269(10) 219(9) 213(10) 54(8) 78(8) 82(8) C(35) 174(8) 192(9) 209(9) 72(7) 60(7) 12(7) C(36) 253(10) 236(10) 211(10) 49(8) 56(8) 37(8) C(37) 285(10) 226(10) 294(11) 60(8) 130(8) 69(8) C(38) 218(10) 245(10) 401(12) 128(9) 123(9) 68(8) C(39) 193(9) 276(10) 309(11) 104(9) 14(8) 23(8) C(40) 204(9) 236(9) 204(9) 60(8) 43(7) 9(8) C(41) 227(9) 205(9) 172(9) 49(7) 52(7) 54(8) C(42) 229(10) 242(10) 231(10) 53(8) 59(8) 37(8) C(43) 259(10) 259(10) 248(10) 15(8) 8(8) 49(8) C(44) 520(14) 319(12) 202(10) 22(9) 107(10) 113(11) C(45) 750(19) 355(13) 328(13) 62(11) 342(13) 32(13) C(46) 480(14) 263(11) 287(12) 40(9) 203(10) -13(10) C(47) 168(8) 211(9) 172(9) 37(7) 52(7) 14(7) C(48) 234(10) 258(10) 318(11) 103(9) 60(8) 29(8) C(49) 269(11) 224(10) 446(13) 54(9) 130(10) -6(9) C(50) 165(9) 397(13) 337(12) -37(10) 72(8) 9(9) C(51) 189(10) 501(14) 364(12) 113(11) 80(9) 125(10) 104 C(52) 210(10) 336(11) 316(11) 128(9) 105(8) 87(9) P(3) 198(2) 208(2) 292(3) 133(2) 65(2) 40(2) P(4) 194(2) 199(2) 241(2) 106(2) 18(2) 13(2) N(8) 245(8) 272(9) 254(9) 115(7) 21(7) -10(7) C(53) 231(9) 184(9) 245(10) 72(8) 85(8) 82(8) C(54) 313(10) 186(9) 277(10) 90(8) 127(8) 85(8) C(55) 388(12) 228(10) 225(10) 82(8) 118(9) 128(9) C(56) 324(11) 233(10) 230(10) 25(8) 51(8) 118(9) C(57) 248(10) 251(10) 294(11) 65(8) 85(8) 55(8) C(58) 247(10) 239(10) 230(10) 88(8) 99(8) 66(8) C(59) 221(10) 249(10) 483(13) 195(10) 129(9) 68(8) C(60) 617(17) 600(17) 750(20) 534(16) 513(16) 439(15) C(61) 840(20) 750(20) 910(20) 650(20) 720(20) 588(19) C(62) 426(14) 427(14) 830(20) 377(15) 308(14) 246(12) C(63) 482(15) 341(13) 492(15) 142(11) 1(12) 199(12) C(64) 405(13) 312(12) 383(13) 90(10) -31(10) 135(10) C(65) 248(10) 222(9) 274(10) 115(8) 71(8) 47(8) C(66) 248(10) 231(10) 242(10) 82(8) 43(8) 49(8) C(67) 291(10) 191(9) 233(10) 62(8) 19(8) 37(8) C(68) 311(11) 205(9) 201(9) 61(8) 45(8) -5(8) C(69) 242(10) 281(11) 378(12) 107(9) 116(9) 18(9) C(70) 276(11) 256(10) 445(13) 157(10) 145(10) 81(9) C(71) 214(9) 245(10) 297(11) 130(8) 30(8) 26(8) C(72) 302(11) 373(12) 363(12) 215(10) 94(9) 121(10) 105 C(73) 393(13) 517(15) 447(14) 261(12) 195(11) 189(12) C(74) 345(13) 493(15) 571(17) 254(13) 172(12) 200(12) C(75) 310(12) 437(14) 500(15) 263(12) 60(10) 151(11) C(76) 267(11) 352(12) 360(12) 201(10) 45(9) 74(9) C(77) 243(9) 212(9) 246(10) 110(8) 65(8) 54(8) C(78) 260(10) 242(10) 266(10) 97(8) 46(8) 26(8) C(79) 341(11) 198(10) 320(11) 79(8) 122(9) 44(9) C(80) 388(12) 248(10) 356(12) 155(9) 155(10) 137(9) C(81) 304(11) 325(11) 306(11) 151(9) 62(9) 125(9) C(82) 247(10) 235(10) 267(10) 97(8) 47(8) 45(8) C(83) 224(9) 192(9) 261(10) 106(8) 16(8) 18(8) C(84) 298(11) 244(10) 249(10) 121(8) 59(8) 36(8) C(85) 379(12) 232(10) 256(11) 82(8) 47(9) 34(9) C(86) 286(11) 232(10) 331(12) 119(9) -10(9) -11(9) C(87) 241(10) 247(10) 416(13) 132(9) 54(9) 38(9) C(88) 248(10) 203(9) 338(11) 91(8) 40(8) 36(8) Cl(1) 276(3) 308(3) 285(3) 105(2) 74(2) 26(2) Cl(2) 537(4) 326(3) 319(3) 78(2) 198(3) 70(3) C(89) 307(12) 273(11) 347(13) 137(10) 125(10) 78(10) Cl(3) 655(11) 556(10) 914(15) -169(10) 211(11) 123(9) Cl(4) 497(9) 722(12) 1400(20) 463(13) 251(11) 84(9) C(90) 750(90) 4800(400) 930(100) -860(170) 160(70) -410(150) Cl(5) 391(7) 283(6) 353(7) 6(5) 149(5) 30(5) Cl(6) 312(9) 379(8) 276(6) 83(5) 83(7) 44(7) 106 C(91) 340(30) 270(20) 280(30) 69(19) 180(20) 40(20) Cl(7) 470(11) 424(10) 537(12) 205(8) 248(9) 242(8) Cl(8) 375(11) 451(12) 860(18) 382(12) 235(11) 183(9) C(92) 300(50) 280(40) 380(40) 150(30) 150(40) 120(40) ______________________________________________________________________________ 107 Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for v19188. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(1) 6247 5127 3292 24 H(2) 7685 6269 4078 26 H(4) 6855 5139 5512 23 H(7) 5674 4110 5724 22 H(9) 3109 1758 4885 31 H(10) 3137 1927 3837 29 H(18) 5897 10584 2266 28 H(19) 4330 10716 1860 36 H(20) 3024 9291 1145 43 H(21) 3279 7752 833 43 H(22) 4868 7630 1172 33 H(24) 5680 7519 2453 28 H(25) 5588 5862 2328 34 H(26) 6549 5139 1731 42 H(27) 7579 6057 1229 47 H(28) 7678 7722 1350 36 H(30) 8601 10620 2819 30 H(31) 9256 11549 3967 38 108 H(32) 8332 11280 4723 39 H(33) 6739 10098 4337 35 H(34) 6070 9167 3192 28 H(36) 7480 11722 2049 30 H(37) 6378 12629 1992 32 H(38) 5254 12342 958 33 H(39) 5255 11177 -16 33 H(40) 6346 10239 38 28 H(42) 6584 8154 335 30 H(43) 6346 7149 -768 34 H(44) 7301 7736 -1433 44 H(45) 8503 9311 -1002 59 H(46) 8778 10314 108 44 H(48) 8889 12086 1163 34 H(49) 10538 13142 1660 40 H(50) 11673 12659 2323 42 H(51) 11178 11093 2470 42 H(52) 9540 10024 1974 33 H(54) 879 5890 4467 30 H(55) 2213 6597 5450 32 H(56) 3676 7774 5472 32 H(57) 3832 8205 4509 33 H(58) 2506 7506 3523 28 H(60) -124 7133 4323 59 109 H(61) -933 8315 4562 74 H(62) -1446 9017 3749 58 H(63) -1126 8573 2708 53 H(64) -341 7375 2456 47 H(66) 771 4373 3118 30 H(67) -218 2840 3144 31 H(68) -1840 2630 3229 31 H(69) -2526 3902 3205 37 H(70) -1556 5434 3169 37 H(72) 1624 5946 673 39 H(73) 2937 5441 391 49 H(74) 3865 4830 1107 52 H(75) 3511 4758 2117 47 H(76) 2193 5255 2407 39 H(78) 1792 7984 2061 32 H(79) 1544 9299 1687 35 H(80) 139 8996 812 37 H(81) -1007 7385 298 36 H(82) -773 6068 674 31 H(84) 245 4138 614 32 H(85) -1210 2786 6 37 H(86) -2674 2685 332 37 H(87) -2698 3919 1262 37 H(88) -1260 5282 1862 33 110 H(89A) 4961 10399 3263 36 H(89B) 3840 10391 3216 36 H(90A) 4734 4771 746 335 H(90B) 4011 4221 1 335 H(91A) 1260 8837 3947 36 H(91B) 2350 9614 4345 36 H(92A) 1844 10212 3050 35 H(92B) 831 9341 2938 35 ________________________________________________________________________________ 111 PPN2Ru(CF3bpy)(CN-BCF) Table 1. Crystal data and structure refinement for D19108. Identification code D19108 Empirical formula C161 H69 B4 F66 N8 O0.50 P4 Ru Formula weight 3645.43 Temperature 100(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 16.024(6) Å α= 73.248(14)°. b = 21.220(6) Å β= 76.541(18)°. c = 23.585(10) Å γ = 79.114(12)°. Volume 7404(5) Å3 Z 2 Density (calculated) 1.635 Mg/m3 Absorption coefficient 0.291 mm-1 F(000) 3626 Crystal size 0.300 x 0.250 x 0.150 mm3 Theta range for data collection 1.523 to 30.508°. Index ranges -22<=h<=22, -29<=k<=30, -33<=l<=33 Reflections collected 246908 Independent reflections 44916 [R(int) = 0.0493] Completeness to theta = 25.242° 99.9 % Absorption correction Semi-empirical from equivalents 112 Max. and min. transmission 1.0000 and 0.9509 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 44916 / 2373 / 2588 Goodness-of-fit on F2 1.011 Final R indices [I>2sigma(I)] R1 = 0.0395, wR2 = 0.0858 R indices (all data) R1 = 0.0588, wR2 = 0.0936 Extinction coefficient n/a Largest diff. peak and hole 0.577 and -0.980 e.Å-3 113 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for D19108. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ N(7) 8780(1) 8990(1) 1524(1) 21(1) P(1) 8214(1) 8410(1) 1853(1) 22(1) C(151) 7122(3) 8630(2) 1696(2) 31(1) C(152) 6447(2) 8284(2) 2075(2) 52(1) C(153) 5624(3) 8440(3) 1934(3) 75(2) C(154) 5459(4) 8940(3) 1435(4) 75(2) C(155) 6135(3) 9261(3) 1042(2) 51(1) C(156) 6951(3) 9127(2) 1192(2) 32(1) C(51B) 7158(7) 8517(6) 1709(4) 38(3) C(52B) 6690(5) 7987(5) 1872(4) 44(2) C(53B) 5862(5) 8092(5) 1753(4) 49(2) C(54B) 5544(9) 8708(6) 1442(9) 65(3) C(55B) 5976(7) 9274(5) 1322(7) 59(3) C(56B) 6826(6) 9145(5) 1421(6) 46(2) C(161) 8125(1) 8146(1) 2656(1) 25(1) C(162) 7464(1) 8461(1) 3020(1) 39(1) C(163) 7423(2) 8286(1) 3635(1) 43(1) C(164) 8032(2) 7807(1) 3888(1) 41(1) C(165) 8691(2) 7496(1) 3532(1) 43(1) 114 C(166) 8740(1) 7668(1) 2911(1) 34(1) C(171) 8732(1) 7712(1) 1559(1) 26(1) C(172) 8443(2) 7096(1) 1810(1) 59(1) C(173) 8831(2) 6570(1) 1563(1) 72(1) C(174) 9493(2) 6658(1) 1069(1) 48(1) C(175) 9780(1) 7268(1) 816(1) 32(1) C(176) 9404(1) 7797(1) 1064(1) 25(1) P(2) 8881(1) 9700(1) 1568(1) 15(1) C(181) 9956(1) 9693(1) 1680(1) 16(1) C(182) 10494(1) 9097(1) 1823(1) 22(1) C(183) 11331(1) 9101(1) 1888(1) 30(1) C(184) 11633(1) 9693(1) 1809(1) 28(1) C(185) 11100(1) 10289(1) 1671(1) 27(1) C(186) 10263(1) 10290(1) 1606(1) 22(1) C(191) 8754(1) 10296(1) 868(1) 18(1) C(192) 8854(1) 10065(1) 355(1) 23(1) C(193) 8783(1) 10514(1) -196(1) 28(1) C(194) 8626(1) 11187(1) -239(1) 30(1) C(195) 8532(1) 11420(1) 267(1) 27(1) C(196) 8595(1) 10976(1) 822(1) 22(1) C(201) 8144(1) 9991(1) 2166(1) 19(1) C(202) 7328(1) 10319(1) 2077(1) 28(1) C(203) 6742(1) 10514(1) 2549(1) 36(1) C(204) 6961(1) 10376(1) 3111(1) 33(1) 115 C(205) 7765(1) 10044(1) 3203(1) 31(1) C(206) 8363(1) 9855(1) 2731(1) 26(1) N(8) 7002(1) 2040(1) 6124(1) 30(1) P(3) 6539(1) 2750(1) 6176(1) 23(1) C(211) 5422(1) 2885(1) 6105(1) 26(1) C(212) 5217(1) 2885(1) 5565(1) 44(1) C(213) 4355(2) 2986(1) 5506(1) 49(1) C(214) 3708(1) 3087(1) 5983(1) 45(1) C(215) 3909(1) 3085(1) 6517(1) 45(1) C(216) 4767(1) 2982(1) 6583(1) 30(1) C(221) 7061(1) 3414(1) 5640(1) 25(1) C(222) 6633(1) 3928(1) 5253(1) 45(1) C(223) 7091(1) 4409(1) 4828(1) 52(1) C(224) 7968(1) 4378(1) 4797(1) 38(1) C(225) 8389(1) 3882(1) 5199(1) 31(1) C(226) 7940(1) 3398(1) 5617(1) 26(1) C(231) 6572(1) 2805(1) 6916(1) 30(1) C(232) 6606(1) 3412(1) 7020(1) 33(1) C(233) 6597(1) 3448(1) 7601(1) 43(1) C(234) 6544(1) 2883(2) 8072(1) 50(1) C(235) 6514(1) 2281(1) 7973(1) 49(1) C(236) 6531(1) 2234(1) 7392(1) 39(1) P(4) 7356(1) 1602(1) 5660(1) 24(1) C(241) 8358(1) 1125(1) 5843(1) 26(1) 116 C(242) 8533(1) 1046(1) 6411(1) 36(1) C(243) 9301(1) 681(1) 6563(1) 40(1) C(244) 9893(1) 402(1) 6150(1) 35(1) C(245) 9728(1) 484(1) 5583(1) 38(1) C(246) 8962(1) 844(1) 5424(1) 34(1) C(251) 6586(1) 1060(1) 5718(1) 31(1) C(252) 6791(1) 567(1) 5411(1) 38(1) C(253) 6165(2) 185(1) 5431(1) 47(1) C(254) 5335(2) 306(1) 5752(1) 50(1) C(255) 5130(1) 784(1) 6059(1) 49(1) C(256) 5754(1) 1164(1) 6052(1) 41(1) C(261) 7590(1) 2048(1) 4879(1) 23(1) C(262) 7044(1) 2087(1) 4484(1) 29(1) C(263) 7220(1) 2462(1) 3895(1) 36(1) C(264) 7934(1) 2800(1) 3693(1) 36(1) C(265) 8472(1) 2773(1) 4083(1) 35(1) C(266) 8306(1) 2395(1) 4674(1) 29(1) Ru(1) 7376(1) 6311(1) 8127(1) 13(1) C(1) 8012(1) 5760(1) 7552(1) 16(1) N(1) 8449(1) 5406(1) 7286(1) 18(1) B(1) 9054(1) 4920(1) 6940(1) 17(1) C(11) 8863(1) 4167(1) 7330(1) 18(1) C(12) 8761(1) 3986(1) 7954(1) 21(1) F(12) 8840(1) 4428(1) 8247(1) 28(1) 117 C(13) 8595(1) 3368(1) 8314(1) 26(1) F(13) 8442(1) 3243(1) 8919(1) 35(1) C(14) 8582(1) 2875(1) 8046(1) 27(1) F(14) 8427(1) 2269(1) 8389(1) 37(1) C(15) 8708(1) 3015(1) 7429(1) 25(1) F(15) 8689(1) 2538(1) 7165(1) 35(1) C(16) 8831(1) 3652(1) 7087(1) 20(1) F(16) 8927(1) 3751(1) 6487(1) 26(1) C(21) 10067(1) 4969(1) 6936(1) 20(1) C(22) 10718(1) 4486(1) 6769(1) 25(1) F(22) 10519(1) 4013(1) 6564(1) 36(1) C(23) 11580(1) 4455(1) 6786(1) 33(1) F(23) 12163(1) 3967(1) 6617(1) 54(1) C(24) 11839(1) 4927(1) 6979(1) 35(1) F(24) 12674(1) 4908(1) 6994(1) 52(1) C(25) 11229(1) 5416(1) 7150(1) 31(1) F(25) 11461(1) 5879(1) 7349(1) 47(1) C(26) 10370(1) 5434(1) 7119(1) 26(1) F(26) 9834(1) 5948(1) 7280(1) 40(1) C(31) 8764(1) 5151(1) 6283(1) 18(1) C(32) 9278(1) 5417(1) 5738(1) 22(1) F(32) 10130(1) 5423(1) 5701(1) 32(1) C(33) 8975(1) 5694(1) 5206(1) 27(1) F(33) 9511(1) 5949(1) 4693(1) 40(1) 118 C(34) 8117(1) 5709(1) 5204(1) 31(1) F(34) 7813(1) 5979(1) 4690(1) 48(1) C(35) 7576(1) 5442(1) 5729(1) 30(1) F(35) 6736(1) 5451(1) 5730(1) 48(1) C(36) 7907(1) 5169(1) 6249(1) 22(1) F(36) 7341(1) 4917(1) 6752(1) 30(1) C(2) 6332(1) 6482(1) 7773(1) 15(1) N(2) 5737(1) 6562(1) 7550(1) 17(1) B(2) 5016(1) 6743(1) 7168(1) 16(1) C(41) 4124(1) 7005(1) 7588(1) 15(1) C(42) 4126(1) 7452(1) 7917(1) 18(1) F(42) 4863(1) 7701(1) 7870(1) 27(1) C(43) 3406(1) 7679(1) 8291(1) 21(1) F(43) 3456(1) 8103(1) 8605(1) 32(1) C(44) 2626(1) 7466(1) 8346(1) 21(1) F(44) 1917(1) 7677(1) 8709(1) 29(1) C(45) 2580(1) 7032(1) 8024(1) 20(1) F(45) 1816(1) 6829(1) 8064(1) 32(1) C(46) 3319(1) 6810(1) 7657(1) 16(1) F(46) 3203(1) 6391(1) 7356(1) 24(1) C(51) 4934(1) 6079(1) 6974(1) 19(1) C(52) 4965(1) 5457(1) 7373(1) 24(1) F(52) 5031(1) 5388(1) 7950(1) 33(1) C(53) 4898(1) 4884(1) 7228(1) 36(1) 119 F(53) 4909(1) 4301(1) 7648(1) 56(1) C(54) 4800(1) 4919(1) 6657(1) 40(1) F(54) 4739(1) 4367(1) 6509(1) 65(1) C(55) 4759(1) 5518(1) 6246(1) 36(1) F(55) 4672(1) 5555(1) 5684(1) 58(1) C(56) 4812(1) 6082(1) 6409(1) 27(1) F(56) 4732(1) 6652(1) 5975(1) 42(1) C(61) 5383(1) 7307(1) 6567(1) 17(1) C(62) 6190(1) 7160(1) 6221(1) 22(1) F(62) 6665(1) 6565(1) 6390(1) 29(1) C(63) 6546(1) 7583(1) 5696(1) 31(1) F(63) 7330(1) 7403(1) 5384(1) 45(1) C(64) 6090(1) 8192(1) 5488(1) 36(1) F(64) 6432(1) 8620(1) 4978(1) 54(1) C(65) 5290(1) 8366(1) 5809(1) 31(1) F(65) 4832(1) 8958(1) 5613(1) 47(1) C(66) 4956(1) 7927(1) 6338(1) 21(1) F(66) 4162(1) 8141(1) 6621(1) 25(1) C(3) 7772(1) 7127(1) 7564(1) 14(1) N(3) 8044(1) 7601(1) 7253(1) 17(1) B(3) 8330(1) 8266(1) 6835(1) 15(1) C(71) 8555(2) 8165(2) 6151(1) 17(1) C(72) 9085(2) 7599(2) 6029(1) 22(1) F(72) 9370(2) 7114(1) 6481(1) 31(1) 120 C(73) 9395(2) 7515(2) 5455(2) 31(1) F(73) 9920(1) 6960(1) 5369(1) 47(1) C(74) 9177(2) 8002(2) 4968(1) 35(1) F(74) 9505(1) 7937(2) 4407(1) 58(1) C(75) 8625(2) 8555(2) 5060(1) 32(1) F(75) 8381(1) 9034(2) 4594(1) 48(1) C(76) 8334(2) 8625(2) 5644(1) 23(1) F(76) 7841(2) 9206(1) 5691(1) 32(1) C(71A) 8552(6) 8293(6) 6113(5) 24(3) C(72A) 8981(9) 7756(7) 5902(5) 30(3) F(72A) 9228(10) 7192(7) 6288(6) 39(3) C(73A) 9220(10) 7756(7) 5292(5) 32(2) F(73A) 9662(9) 7219(6) 5134(6) 62(3) C(74A) 9002(9) 8322(7) 4890(5) 33(2) F(74A) 9242(9) 8353(8) 4294(4) 62(3) C(75A) 8545(8) 8861(7) 5063(4) 30(2) F(75A) 8317(6) 9428(7) 4658(4) 52(3) C(76A) 8314(10) 8845(7) 5673(5) 22(2) F(76A) 7930(8) 9410(6) 5816(5) 40(3) C(81) 9223(1) 8371(1) 7014(1) 16(1) C(82) 9940(1) 8604(1) 6601(1) 19(1) F(82) 9935(1) 8808(1) 6004(1) 28(1) C(83) 10702(1) 8654(1) 6758(1) 22(1) F(83) 11364(1) 8889(1) 6328(1) 32(1) 121 C(84) 10773(1) 8475(1) 7354(1) 24(1) F(84) 11504(1) 8517(1) 7517(1) 34(1) C(85) 10076(1) 8256(1) 7785(1) 22(1) F(85) 10124(1) 8096(1) 8371(1) 31(1) C(86) 9324(1) 8216(1) 7610(1) 18(1) F(86) 8656(1) 8026(1) 8063(1) 24(1) C(91) 7505(1) 8824(1) 6964(1) 16(1) C(92) 7497(1) 9379(1) 7163(1) 23(1) F(92) 8230(1) 9528(1) 7250(1) 40(1) C(93) 6751(1) 9809(1) 7290(1) 26(1) F(93) 6786(1) 10342(1) 7481(1) 46(1) C(94) 5972(1) 9692(1) 7226(1) 23(1) F(94) 5246(1) 10096(1) 7361(1) 31(1) C(95) 5945(1) 9154(1) 7020(1) 21(1) F(95) 5194(1) 9040(1) 6931(1) 32(1) C(96) 6699(1) 8739(1) 6899(1) 18(1) F(96) 6630(1) 8226(1) 6691(1) 26(1) C(4) 6843(1) 6801(1) 8767(1) 17(1) N(4) 6630(1) 7018(1) 9181(1) 20(1) B(4) 6431(1) 7300(1) 9745(1) 20(1) C(101) 6386(2) 6686(2) 10367(2) 19(1) C(102) 6468(3) 6785(2) 10905(2) 30(1) F(102) 6475(3) 7406(2) 10940(1) 50(1) C(103) 6574(3) 6278(2) 11415(2) 38(1) 122 F(103) 6669(3) 6416(2) 11918(1) 68(1) C(104) 6571(3) 5631(2) 11412(2) 40(1) F(104) 6695(3) 5133(2) 11897(2) 64(1) C(105) 6443(5) 5502(2) 10909(3) 41(1) F(105) 6413(4) 4876(2) 10893(2) 79(2) C(106) 6334(6) 6027(3) 10404(3) 32(1) F(106) 6169(4) 5848(2) 9938(2) 58(1) C(01B) 6448(4) 6639(5) 10293(4) 29(2) C(02B) 6748(5) 6628(4) 10811(3) 29(2) F(02B) 6948(6) 7180(4) 10884(2) 52(2) C(03B) 6848(5) 6051(4) 11278(3) 36(2) F(03B) 7142(5) 6078(5) 11757(3) 64(2) C(04B) 6645(6) 5483(4) 11234(4) 36(2) F(04B) 6760(5) 4928(4) 11678(4) 59(2) C(05B) 6287(9) 5494(5) 10764(5) 35(2) F(05B) 6045(6) 4935(4) 10739(4) 58(2) C(06B) 6190(11) 6055(5) 10317(6) 25(2) F(06B) 5843(5) 6023(4) 9865(3) 38(2) C(111) 7296(1) 7647(1) 9692(1) 24(1) C(112) 8113(1) 7282(1) 9620(1) 26(1) F(112) 8196(1) 6642(1) 9594(1) 31(1) C(113) 8872(1) 7520(1) 9583(1) 31(1) F(113) 9637(1) 7135(1) 9511(1) 41(1) C(114) 8833(1) 8156(1) 9627(1) 34(1) 123 F(114) 9562(1) 8404(1) 9596(1) 45(1) C(115) 8045(1) 8538(1) 9712(1) 34(1) F(115) 7999(1) 9157(1) 9770(1) 47(1) C(116) 7297(1) 8281(1) 9743(1) 30(1) F(116) 6549(1) 8688(1) 9833(1) 43(1) C(121) 5548(1) 7817(1) 9687(1) 20(1) C(122) 5484(1) 8307(1) 9156(1) 23(1) F(122) 6181(1) 8378(1) 8702(1) 36(1) C(123) 4751(1) 8746(1) 9058(1) 26(1) F(123) 4729(1) 9205(1) 8533(1) 42(1) C(124) 4027(1) 8719(1) 9511(1) 29(1) F(124) 3313(1) 9152(1) 9424(1) 42(1) C(125) 4056(1) 8248(1) 10045(1) 34(1) F(125) 3354(1) 8214(1) 10492(1) 60(1) C(126) 4800(1) 7812(1) 10122(1) 29(1) F(126) 4766(1) 7361(1) 10662(1) 49(1) N(5) 8482(1) 6021(1) 8526(1) 16(1) C(131) 9170(1) 6350(1) 8366(1) 21(1) C(132) 9931(1) 6089(1) 8580(1) 23(1) C(133) 9972(1) 5462(1) 8970(1) 21(1) C(141) 10817(1) 5142(1) 9164(1) 28(1) F(131) 11417(8) 5022(10) 8706(5) 58(2) F(132) 10740(6) 4598(4) 9616(4) 30(2) F(133) 11121(10) 5591(8) 9346(5) 45(2) 124 F(31B) 11375(9) 4925(7) 8716(6) 33(2) F(32B) 10726(10) 4581(6) 9607(6) 39(3) F(33B) 11206(10) 5501(9) 9375(6) 29(2) C(134) 9255(1) 5128(1) 9158(1) 20(1) C(135) 8507(1) 5424(1) 8932(1) 17(1) C(136) 7708(1) 5107(1) 9097(1) 18(1) C(137) 7595(1) 4519(1) 9541(1) 24(1) C(138) 6832(1) 4256(1) 9652(1) 29(1) C(142) 6695(2) 3607(1) 10115(1) 47(1) F(134) 6483(6) 3179(3) 9866(4) 84(2) F(135) 6082(6) 3645(6) 10571(4) 79(3) F(136) 7418(3) 3286(2) 10310(3) 54(1) F(34B) 6776(10) 3118(5) 9889(6) 89(3) F(35B) 5903(7) 3681(9) 10447(6) 80(3) F(36B) 7193(10) 3511(8) 10520(6) 97(4) C(139) 6191(1) 4583(1) 9328(1) 30(1) C(140) 6339(1) 5169(1) 8897(1) 24(1) N(6) 7083(1) 5427(1) 8778(1) 17(1) O(1S) 3570(20) 9085(9) 868(12) 171(8) C(11S) 3416(10) 9731(9) 667(8) 66(4) C(12S) 3730(17) 10080(11) 1077(9) 86(6) O(2S) 3915(14) 9845(11) 827(10) 162(8) C(21S) 4557(15) 10209(13) 354(11) 103(6) C(22S) 5050(18) 9749(16) -37(12) 120(8) 125 O(3S) 4341(11) 9795(9) 266(8) 85(4) C(31S) 4127(16) 9213(14) 603(11) 81(5) C(32S) 3500(20) 9279(14) 1189(12) 112(8) ________________________________________________________________________________ 126 Table 3. Bond lengths [Å] and angles [°] for D19108. _____________________________________________________ N(7)-P(1) 1.5762(14) N(7)-P(2) 1.5819(14) P(1)-C(51B) 1.763(11) P(1)-C(161) 1.7931(19) P(1)-C(171) 1.7932(18) P(1)-C(151) 1.819(5) C(151)-C(156) 1.384(5) C(151)-C(152) 1.405(5) C(152)-C(153) 1.391(5) C(152)-H(152) 0.9500 C(153)-C(154) 1.378(7) C(153)-H(153) 0.9500 C(154)-C(155) 1.396(7) C(154)-H(154) 0.9500 C(155)-C(156) 1.391(5) C(155)-H(155) 0.9500 C(156)-H(156) 0.9500 C(51B)-C(56B) 1.377(11) C(51B)-C(52B) 1.383(11) C(52B)-C(53B) 1.385(9) C(52B)-H(52B) 0.9500 C(53B)-C(54B) 1.370(11) 127 C(53B)-H(53B) 0.9500 C(54B)-C(55B) 1.425(11) C(54B)-H(54B) 0.9500 C(55B)-C(56B) 1.398(10) C(55B)-H(55B) 0.9500 C(56B)-H(56B) 0.9500 C(161)-C(166) 1.383(3) C(161)-C(162) 1.394(3) C(162)-C(163) 1.379(3) C(162)-H(162) 0.9500 C(163)-C(164) 1.373(3) C(163)-H(163) 0.9500 C(164)-C(165) 1.378(3) C(164)-H(164) 0.9500 C(165)-C(166) 1.391(3) C(165)-H(165) 0.9500 C(166)-H(166) 0.9500 C(171)-C(176) 1.387(2) C(171)-C(172) 1.389(3) C(172)-C(173) 1.384(3) C(172)-H(172) 0.9500 C(173)-C(174) 1.376(4) C(173)-H(173) 0.9500 C(174)-C(175) 1.377(3) 128 C(174)-H(174) 0.9500 C(175)-C(176) 1.386(2) C(175)-H(175) 0.9500 C(176)-H(176) 0.9500 P(2)-C(201) 1.7936(16) P(2)-C(191) 1.7960(16) P(2)-C(181) 1.7975(17) C(181)-C(182) 1.392(2) C(181)-C(186) 1.395(2) C(182)-C(183) 1.386(2) C(182)-H(182) 0.9500 C(183)-C(184) 1.378(3) C(183)-H(183) 0.9500 C(184)-C(185) 1.385(3) C(184)-H(184) 0.9500 C(185)-C(186) 1.384(2) C(185)-H(185) 0.9500 C(186)-H(186) 0.9500 C(191)-C(196) 1.395(2) C(191)-C(192) 1.395(2) C(192)-C(193) 1.387(2) C(192)-H(192) 0.9500 C(193)-C(194) 1.380(3) C(193)-H(193) 0.9500 129 C(194)-C(195) 1.386(3) C(194)-H(194) 0.9500 C(195)-C(196) 1.388(2) C(195)-H(195) 0.9500 C(196)-H(196) 0.9500 C(201)-C(206) 1.392(2) C(201)-C(202) 1.392(2) C(202)-C(203) 1.388(2) C(202)-H(202) 0.9500 C(203)-C(204) 1.385(3) C(203)-H(203) 0.9500 C(204)-C(205) 1.380(3) C(204)-H(204) 0.9500 C(205)-C(206) 1.391(2) C(205)-H(205) 0.9500 C(206)-H(206) 0.9500 N(8)-P(4) 1.5745(17) N(8)-P(3) 1.5754(17) P(3)-C(221) 1.7919(18) P(3)-C(231) 1.795(2) P(3)-C(211) 1.7964(18) C(211)-C(216) 1.384(3) C(211)-C(212) 1.387(3) C(212)-C(213) 1.391(3) 130 C(212)-H(212) 0.9500 C(213)-C(214) 1.379(4) C(213)-H(213) 0.9500 C(214)-C(215) 1.369(4) C(214)-H(214) 0.9500 C(215)-C(216) 1.389(3) C(215)-H(215) 0.9500 C(216)-H(216) 0.9500 C(221)-C(222) 1.389(3) C(221)-C(226) 1.391(2) C(222)-C(223) 1.391(3) C(222)-H(222) 0.9500 C(223)-C(224) 1.380(3) C(223)-H(223) 0.9500 C(224)-C(225) 1.384(3) C(224)-H(224) 0.9500 C(225)-C(226) 1.382(3) C(225)-H(225) 0.9500 C(226)-H(226) 0.9500 C(231)-C(232) 1.392(3) C(231)-C(236) 1.395(3) C(232)-C(233) 1.392(3) C(232)-H(232) 0.9500 C(233)-C(234) 1.381(4) 131 C(233)-H(233) 0.9500 C(234)-C(235) 1.375(4) C(234)-H(234) 0.9500 C(235)-C(236) 1.397(3) C(235)-H(235) 0.9500 C(236)-H(236) 0.9500 P(4)-C(251) 1.799(2) P(4)-C(261) 1.7992(18) P(4)-C(241) 1.8007(17) C(241)-C(242) 1.390(3) C(241)-C(246) 1.395(3) C(242)-C(243) 1.389(3) C(242)-H(242) 0.9500 C(243)-C(244) 1.374(3) C(243)-H(243) 0.9500 C(244)-C(245) 1.381(3) C(244)-H(244) 0.9500 C(245)-C(246) 1.388(3) C(245)-H(245) 0.9500 C(246)-H(246) 0.9500 C(251)-C(252) 1.386(3) C(251)-C(256) 1.394(3) C(252)-C(253) 1.389(3) C(252)-H(252) 0.9500 132 C(253)-C(254) 1.386(4) C(253)-H(253) 0.9500 C(254)-C(255) 1.358(4) C(254)-H(254) 0.9500 C(255)-C(256) 1.395(3) C(255)-H(255) 0.9500 C(256)-H(256) 0.9500 C(261)-C(262) 1.395(2) C(261)-C(266) 1.395(2) C(262)-C(263) 1.382(3) C(262)-H(262) 0.9500 C(263)-C(264) 1.381(3) C(263)-H(263) 0.9500 C(264)-C(265) 1.383(3) C(264)-H(264) 0.9500 C(265)-C(266) 1.386(3) C(265)-H(265) 0.9500 C(266)-H(266) 0.9500 Ru(1)-C(3) 1.9640(16) Ru(1)-C(2) 1.9687(16) Ru(1)-C(4) 2.0137(16) Ru(1)-C(1) 2.0167(16) Ru(1)-N(6) 2.1043(14) Ru(1)-N(5) 2.1052(14) 133 C(1)-N(1) 1.1494(19) N(1)-B(1) 1.550(2) B(1)-C(31) 1.634(2) B(1)-C(11) 1.643(2) B(1)-C(21) 1.643(2) C(11)-C(12) 1.387(2) C(11)-C(16) 1.387(2) C(12)-F(12) 1.3546(19) C(12)-C(13) 1.377(2) C(13)-F(13) 1.346(2) C(13)-C(14) 1.374(3) C(14)-F(14) 1.3406(19) C(14)-C(15) 1.373(3) C(15)-F(15) 1.3411(19) C(15)-C(16) 1.384(2) C(16)-F(16) 1.3459(19) C(21)-C(26) 1.386(2) C(21)-C(22) 1.390(2) C(22)-F(22) 1.347(2) C(22)-C(23) 1.380(2) C(23)-F(23) 1.343(2) C(23)-C(24) 1.375(3) C(24)-F(24) 1.339(2) C(24)-C(25) 1.367(3) 134 C(25)-F(25) 1.344(2) C(25)-C(26) 1.389(3) C(26)-F(26) 1.342(2) C(31)-C(32) 1.383(2) C(31)-C(36) 1.387(2) C(32)-F(32) 1.3508(19) C(32)-C(33) 1.381(2) C(33)-F(33) 1.344(2) C(33)-C(34) 1.371(3) C(34)-F(34) 1.343(2) C(34)-C(35) 1.374(3) C(35)-F(35) 1.342(2) C(35)-C(36) 1.378(2) C(36)-F(36) 1.3531(19) C(2)-N(2) 1.155(2) N(2)-B(2) 1.554(2) B(2)-C(51) 1.636(2) B(2)-C(61) 1.639(2) B(2)-C(41) 1.640(2) C(41)-C(46) 1.389(2) C(41)-C(42) 1.389(2) C(42)-F(42) 1.3511(18) C(42)-C(43) 1.380(2) C(43)-F(43) 1.3442(18) 135 C(43)-C(44) 1.374(2) C(44)-F(44) 1.3416(17) C(44)-C(45) 1.373(2) C(45)-F(45) 1.3463(18) C(45)-C(46) 1.385(2) C(46)-F(46) 1.3475(18) C(51)-C(52) 1.384(2) C(51)-C(56) 1.388(2) C(52)-F(52) 1.353(2) C(52)-C(53) 1.383(2) C(53)-F(53) 1.344(2) C(53)-C(54) 1.369(3) C(54)-F(54) 1.341(2) C(54)-C(55) 1.359(3) C(55)-F(55) 1.342(2) C(55)-C(56) 1.381(3) C(56)-F(56) 1.348(2) C(61)-C(66) 1.383(2) C(61)-C(62) 1.393(2) C(62)-F(62) 1.349(2) C(62)-C(63) 1.375(2) C(63)-F(63) 1.347(2) C(63)-C(64) 1.375(3) C(64)-F(64) 1.348(2) 136 C(64)-C(65) 1.372(3) C(65)-F(65) 1.344(2) C(65)-C(66) 1.384(2) C(66)-F(66) 1.3536(19) C(3)-N(3) 1.1553(19) N(3)-B(3) 1.551(2) B(3)-C(91) 1.634(2) B(3)-C(71) 1.638(3) B(3)-C(71A) 1.644(12) B(3)-C(81) 1.652(2) C(71)-C(76) 1.380(3) C(71)-C(72) 1.395(3) C(72)-F(72) 1.349(3) C(72)-C(73) 1.380(3) C(73)-F(73) 1.349(3) C(73)-C(74) 1.369(4) C(74)-F(74) 1.343(3) C(74)-C(75) 1.367(4) C(75)-F(75) 1.343(3) C(75)-C(76) 1.388(4) C(76)-F(76) 1.350(3) C(71A)-C(72A) 1.375(12) C(71A)-C(76A) 1.381(11) C(72A)-F(72A) 1.334(11) 137 C(72A)-C(73A) 1.399(11) C(73A)-F(73A) 1.327(11) C(73A)-C(74A) 1.342(11) C(74A)-C(75A) 1.351(11) C(74A)-F(74A) 1.353(11) C(75A)-F(75A) 1.353(11) C(75A)-C(76A) 1.391(11) C(76A)-F(76A) 1.338(11) C(81)-C(82) 1.389(2) C(81)-C(86) 1.389(2) C(82)-F(82) 1.3501(19) C(82)-C(83) 1.385(2) C(83)-F(83) 1.3454(19) C(83)-C(84) 1.372(2) C(84)-F(84) 1.3402(18) C(84)-C(85) 1.376(2) C(85)-F(85) 1.3430(19) C(85)-C(86) 1.384(2) C(86)-F(86) 1.3542(18) C(91)-C(92) 1.385(2) C(91)-C(96) 1.385(2) C(92)-F(92) 1.3453(19) C(92)-C(93) 1.389(2) C(93)-F(93) 1.3465(19) 138 C(93)-C(94) 1.366(2) C(94)-F(94) 1.3410(17) C(94)-C(95) 1.374(2) C(95)-F(95) 1.3447(19) C(95)-C(96) 1.378(2) C(96)-F(96) 1.3464(18) C(4)-N(4) 1.150(2) N(4)-B(4) 1.556(2) B(4)-C(01B) 1.612(10) B(4)-C(121) 1.625(2) B(4)-C(111) 1.652(2) B(4)-C(101) 1.656(5) C(101)-C(102) 1.383(5) C(101)-C(106) 1.393(6) C(102)-F(102) 1.346(4) C(102)-C(103) 1.382(5) C(103)-F(103) 1.348(4) C(103)-C(104) 1.376(6) C(104)-F(104) 1.339(5) C(104)-C(105) 1.360(6) C(105)-F(105) 1.350(5) C(105)-C(106) 1.395(6) C(106)-F(106) 1.357(5) C(01B)-C(06B) 1.360(11) 139 C(01B)-C(02B) 1.405(10) C(02B)-F(02B) 1.338(8) C(02B)-C(03B) 1.402(8) C(03B)-F(03B) 1.340(7) C(03B)-C(04B) 1.344(9) C(04B)-F(04B) 1.348(9) C(04B)-C(05B) 1.354(9) C(05B)-F(05B) 1.336(10) C(05B)-C(06B) 1.355(10) C(06B)-F(06B) 1.336(9) C(111)-C(116) 1.385(3) C(111)-C(112) 1.390(3) C(112)-F(112) 1.356(2) C(112)-C(113) 1.378(3) C(113)-F(113) 1.343(2) C(113)-C(114) 1.372(3) C(114)-F(114) 1.347(2) C(114)-C(115) 1.372(3) C(115)-F(115) 1.345(2) C(115)-C(116) 1.388(3) C(116)-F(116) 1.350(2) C(121)-C(126) 1.383(2) C(121)-C(122) 1.390(2) C(122)-F(122) 1.3520(19) 140 C(122)-C(123) 1.375(2) C(123)-F(123) 1.3401(19) C(123)-C(124) 1.381(2) C(124)-F(124) 1.340(2) C(124)-C(125) 1.369(3) C(125)-F(125) 1.348(2) C(125)-C(126) 1.378(3) C(126)-F(126) 1.351(2) N(5)-C(131) 1.338(2) N(5)-C(135) 1.3511(19) C(131)-C(132) 1.384(2) C(131)-H(131) 0.9500 C(132)-C(133) 1.382(2) C(132)-H(132) 0.9500 C(133)-C(134) 1.381(2) C(133)-C(141) 1.505(2) C(141)-F(131) 1.318(7) C(141)-F(33B) 1.325(9) C(141)-F(132) 1.329(7) C(141)-F(32B) 1.345(10) C(141)-F(31B) 1.346(8) C(141)-F(133) 1.355(8) C(134)-C(135) 1.391(2) C(134)-H(134) 0.9500 141 C(135)-C(136) 1.477(2) C(136)-N(6) 1.3534(19) C(136)-C(137) 1.390(2) C(137)-C(138) 1.379(2) C(137)-H(137) 0.9500 C(138)-C(139) 1.383(3) C(138)-C(142) 1.507(2) C(142)-F(34B) 1.270(9) C(142)-F(135) 1.287(7) C(142)-F(36B) 1.331(7) C(142)-F(35B) 1.335(10) C(142)-F(136) 1.336(4) C(142)-F(134) 1.342(6) C(139)-C(140) 1.380(2) C(139)-H(139) 0.9500 C(140)-N(6) 1.344(2) C(140)-H(140) 0.9500 O(1S)-C(11S) 1.311(17) O(1S)-H(1S) 0.8400 C(11S)-C(12S) 1.585(16) C(11S)-H(11A) 0.9900 C(11S)-H(11B) 0.9900 C(12S)-H(12A) 0.9800 C(12S)-H(12B) 0.9800 142 C(12S)-H(12C) 0.9800 O(2S)-C(21S) 1.472(18) O(2S)-H(2S) 0.8400 C(21S)-C(22S) 1.520(17) C(21S)-H(21A) 0.9900 C(21S)-H(21B) 0.9900 C(22S)-H(22A) 0.9800 C(22S)-H(22B) 0.9800 C(22S)-H(22C) 0.9800 O(3S)-C(31S) 1.32(3) O(3S)-H(3S) 0.8400 C(31S)-C(32S) 1.536(17) C(31S)-H(31A) 0.9900 C(31S)-H(31B) 0.9900 C(32S)-H(32A) 0.9800 C(32S)-H(32B) 0.9800 C(32S)-H(32C) 0.9800 P(1)-N(7)-P(2) 140.07(9) N(7)-P(1)-C(51B) 117.5(4) N(7)-P(1)-C(161) 114.94(8) C(51B)-P(1)-C(161) 106.7(3) N(7)-P(1)-C(171) 106.50(8) C(51B)-P(1)-C(171) 102.7(3) 143 C(161)-P(1)-C(171) 107.36(8) N(7)-P(1)-C(151) 111.45(16) C(161)-P(1)-C(151) 107.53(16) C(171)-P(1)-C(151) 108.86(16) C(156)-C(151)-C(152) 119.3(4) C(156)-C(151)-P(1) 120.3(3) C(152)-C(151)-P(1) 120.4(3) C(153)-C(152)-C(151) 119.6(4) C(153)-C(152)-H(152) 120.2 C(151)-C(152)-H(152) 120.2 C(154)-C(153)-C(152) 120.7(4) C(154)-C(153)-H(153) 119.7 C(152)-C(153)-H(153) 119.7 C(153)-C(154)-C(155) 119.8(5) C(153)-C(154)-H(154) 120.1 C(155)-C(154)-H(154) 120.1 C(156)-C(155)-C(154) 119.5(4) C(156)-C(155)-H(155) 120.3 C(154)-C(155)-H(155) 120.3 C(151)-C(156)-C(155) 120.7(4) C(151)-C(156)-H(156) 119.6 C(155)-C(156)-H(156) 119.6 C(56B)-C(51B)-C(52B) 121.7(10) C(56B)-C(51B)-P(1) 117.5(8) 144 C(52B)-C(51B)-P(1) 120.8(8) C(51B)-C(52B)-C(53B) 119.1(8) C(51B)-C(52B)-H(52B) 120.4 C(53B)-C(52B)-H(52B) 120.4 C(54B)-C(53B)-C(52B) 119.5(8) C(54B)-C(53B)-H(53B) 120.3 C(52B)-C(53B)-H(53B) 120.3 C(53B)-C(54B)-C(55B) 122.0(10) C(53B)-C(54B)-H(54B) 119.0 C(55B)-C(54B)-H(54B) 119.0 C(56B)-C(55B)-C(54B) 116.0(9) C(56B)-C(55B)-H(55B) 122.0 C(54B)-C(55B)-H(55B) 122.0 C(51B)-C(56B)-C(55B) 120.5(9) C(51B)-C(56B)-H(56B) 119.8 C(55B)-C(56B)-H(56B) 119.8 C(166)-C(161)-C(162) 120.03(17) C(166)-C(161)-P(1) 120.38(13) C(162)-C(161)-P(1) 119.44(15) C(163)-C(162)-C(161) 119.5(2) C(163)-C(162)-H(162) 120.2 C(161)-C(162)-H(162) 120.2 C(164)-C(163)-C(162) 120.30(19) C(164)-C(163)-H(163) 119.8 145 C(162)-C(163)-H(163) 119.8 C(163)-C(164)-C(165) 120.70(19) C(163)-C(164)-H(164) 119.6 C(165)-C(164)-H(164) 119.6 C(164)-C(165)-C(166) 119.6(2) C(164)-C(165)-H(165) 120.2 C(166)-C(165)-H(165) 120.2 C(161)-C(166)-C(165) 119.82(19) C(161)-C(166)-H(166) 120.1 C(165)-C(166)-H(166) 120.1 C(176)-C(171)-C(172) 119.92(17) C(176)-C(171)-P(1) 119.60(13) C(172)-C(171)-P(1) 120.43(16) C(173)-C(172)-C(171) 119.6(2) C(173)-C(172)-H(172) 120.2 C(171)-C(172)-H(172) 120.2 C(174)-C(173)-C(172) 120.2(2) C(174)-C(173)-H(173) 119.9 C(172)-C(173)-H(173) 119.9 C(173)-C(174)-C(175) 120.48(19) C(173)-C(174)-H(174) 119.8 C(175)-C(174)-H(174) 119.8 C(174)-C(175)-C(176) 119.78(19) C(174)-C(175)-H(175) 120.1 146 C(176)-C(175)-H(175) 120.1 C(175)-C(176)-C(171) 119.99(17) C(175)-C(176)-H(176) 120.0 C(171)-C(176)-H(176) 120.0 N(7)-P(2)-C(201) 115.59(7) N(7)-P(2)-C(191) 109.14(8) C(201)-P(2)-C(191) 108.21(7) N(7)-P(2)-C(181) 109.29(7) C(201)-P(2)-C(181) 106.93(7) C(191)-P(2)-C(181) 107.38(7) C(182)-C(181)-C(186) 119.55(14) C(182)-C(181)-P(2) 120.57(12) C(186)-C(181)-P(2) 119.86(11) C(183)-C(182)-C(181) 119.82(16) C(183)-C(182)-H(182) 120.1 C(181)-C(182)-H(182) 120.1 C(184)-C(183)-C(182) 120.34(16) C(184)-C(183)-H(183) 119.8 C(182)-C(183)-H(183) 119.8 C(183)-C(184)-C(185) 120.28(16) C(183)-C(184)-H(184) 119.9 C(185)-C(184)-H(184) 119.9 C(186)-C(185)-C(184) 119.89(16) C(186)-C(185)-H(185) 120.1 147 C(184)-C(185)-H(185) 120.1 C(185)-C(186)-C(181) 120.12(15) C(185)-C(186)-H(186) 119.9 C(181)-C(186)-H(186) 119.9 C(196)-C(191)-C(192) 119.89(14) C(196)-C(191)-P(2) 121.64(12) C(192)-C(191)-P(2) 118.41(12) C(193)-C(192)-C(191) 119.80(16) C(193)-C(192)-H(192) 120.1 C(191)-C(192)-H(192) 120.1 C(194)-C(193)-C(192) 120.10(16) C(194)-C(193)-H(193) 119.9 C(192)-C(193)-H(193) 119.9 C(193)-C(194)-C(195) 120.51(16) C(193)-C(194)-H(194) 119.7 C(195)-C(194)-H(194) 119.7 C(194)-C(195)-C(196) 119.95(17) C(194)-C(195)-H(195) 120.0 C(196)-C(195)-H(195) 120.0 C(195)-C(196)-C(191) 119.74(16) C(195)-C(196)-H(196) 120.1 C(191)-C(196)-H(196) 120.1 C(206)-C(201)-C(202) 119.74(14) C(206)-C(201)-P(2) 120.25(12) 148 C(202)-C(201)-P(2) 119.90(13) C(203)-C(202)-C(201) 119.76(17) C(203)-C(202)-H(202) 120.1 C(201)-C(202)-H(202) 120.1 C(204)-C(203)-C(202) 120.32(17) C(204)-C(203)-H(203) 119.8 C(202)-C(203)-H(203) 119.8 C(205)-C(204)-C(203) 120.07(16) C(205)-C(204)-H(204) 120.0 C(203)-C(204)-H(204) 120.0 C(204)-C(205)-C(206) 120.14(17) C(204)-C(205)-H(205) 119.9 C(206)-C(205)-H(205) 119.9 C(205)-C(206)-C(201) 119.95(16) C(205)-C(206)-H(206) 120.0 C(201)-C(206)-H(206) 120.0 P(4)-N(8)-P(3) 142.43(10) N(8)-P(3)-C(221) 113.61(8) N(8)-P(3)-C(231) 106.67(9) C(221)-P(3)-C(231) 107.66(9) N(8)-P(3)-C(211) 113.00(9) C(221)-P(3)-C(211) 107.92(8) C(231)-P(3)-C(211) 107.71(8) C(216)-C(211)-C(212) 119.73(17) 149 C(216)-C(211)-P(3) 120.89(14) C(212)-C(211)-P(3) 119.38(14) C(211)-C(212)-C(213) 119.9(2) C(211)-C(212)-H(212) 120.1 C(213)-C(212)-H(212) 120.1 C(214)-C(213)-C(212) 119.9(2) C(214)-C(213)-H(213) 120.0 C(212)-C(213)-H(213) 120.0 C(215)-C(214)-C(213) 120.28(18) C(215)-C(214)-H(214) 119.9 C(213)-C(214)-H(214) 119.9 C(214)-C(215)-C(216) 120.3(2) C(214)-C(215)-H(215) 119.8 C(216)-C(215)-H(215) 119.8 C(211)-C(216)-C(215) 119.9(2) C(211)-C(216)-H(216) 120.1 C(215)-C(216)-H(216) 120.1 C(222)-C(221)-C(226) 119.77(17) C(222)-C(221)-P(3) 123.18(14) C(226)-C(221)-P(3) 117.06(13) C(221)-C(222)-C(223) 119.89(18) C(221)-C(222)-H(222) 120.1 C(223)-C(222)-H(222) 120.1 C(224)-C(223)-C(222) 119.9(2) 150 C(224)-C(223)-H(223) 120.0 C(222)-C(223)-H(223) 120.0 C(223)-C(224)-C(225) 120.25(18) C(223)-C(224)-H(224) 119.9 C(225)-C(224)-H(224) 119.9 C(226)-C(225)-C(224) 120.14(17) C(226)-C(225)-H(225) 119.9 C(224)-C(225)-H(225) 119.9 C(225)-C(226)-C(221) 119.95(17) C(225)-C(226)-H(226) 120.0 C(221)-C(226)-H(226) 120.0 C(232)-C(231)-C(236) 120.26(18) C(232)-C(231)-P(3) 120.65(14) C(236)-C(231)-P(3) 119.05(16) C(233)-C(232)-C(231) 119.7(2) C(233)-C(232)-H(232) 120.1 C(231)-C(232)-H(232) 120.1 C(234)-C(233)-C(232) 119.9(2) C(234)-C(233)-H(233) 120.1 C(232)-C(233)-H(233) 120.1 C(235)-C(234)-C(233) 120.8(2) C(235)-C(234)-H(234) 119.6 C(233)-C(234)-H(234) 119.6 C(234)-C(235)-C(236) 120.2(2) 151 C(234)-C(235)-H(235) 119.9 C(236)-C(235)-H(235) 119.9 C(231)-C(236)-C(235) 119.2(2) C(231)-C(236)-H(236) 120.4 C(235)-C(236)-H(236) 120.4 N(8)-P(4)-C(251) 110.02(9) N(8)-P(4)-C(261) 116.07(8) C(251)-P(4)-C(261) 106.42(8) N(8)-P(4)-C(241) 107.25(8) C(251)-P(4)-C(241) 110.30(9) C(261)-P(4)-C(241) 106.70(8) C(242)-C(241)-C(246) 119.73(16) C(242)-C(241)-P(4) 118.90(13) C(246)-C(241)-P(4) 121.37(14) C(243)-C(242)-C(241) 120.00(18) C(243)-C(242)-H(242) 120.0 C(241)-C(242)-H(242) 120.0 C(244)-C(243)-C(242) 120.16(19) C(244)-C(243)-H(243) 119.9 C(242)-C(243)-H(243) 119.9 C(243)-C(244)-C(245) 120.19(17) C(243)-C(244)-H(244) 119.9 C(245)-C(244)-H(244) 119.9 C(244)-C(245)-C(246) 120.48(18) 152 C(244)-C(245)-H(245) 119.8 C(246)-C(245)-H(245) 119.8 C(245)-C(246)-C(241) 119.43(18) C(245)-C(246)-H(246) 120.3 C(241)-C(246)-H(246) 120.3 C(252)-C(251)-C(256) 119.86(19) C(252)-C(251)-P(4) 121.13(15) C(256)-C(251)-P(4) 118.91(17) C(251)-C(252)-C(253) 119.9(2) C(251)-C(252)-H(252) 120.0 C(253)-C(252)-H(252) 120.0 C(254)-C(253)-C(252) 119.6(2) C(254)-C(253)-H(253) 120.2 C(252)-C(253)-H(253) 120.2 C(255)-C(254)-C(253) 121.0(2) C(255)-C(254)-H(254) 119.5 C(253)-C(254)-H(254) 119.5 C(254)-C(255)-C(256) 120.2(2) C(254)-C(255)-H(255) 119.9 C(256)-C(255)-H(255) 119.9 C(251)-C(256)-C(255) 119.5(2) C(251)-C(256)-H(256) 120.3 C(255)-C(256)-H(256) 120.3 C(262)-C(261)-C(266) 119.35(16) 153 C(262)-C(261)-P(4) 121.52(13) C(266)-C(261)-P(4) 119.02(13) C(263)-C(262)-C(261) 119.86(17) C(263)-C(262)-H(262) 120.1 C(261)-C(262)-H(262) 120.1 C(264)-C(263)-C(262) 120.53(18) C(264)-C(263)-H(263) 119.7 C(262)-C(263)-H(263) 119.7 C(263)-C(264)-C(265) 120.09(18) C(263)-C(264)-H(264) 120.0 C(265)-C(264)-H(264) 120.0 C(264)-C(265)-C(266) 119.93(17) C(264)-C(265)-H(265) 120.0 C(266)-C(265)-H(265) 120.0 C(265)-C(266)-C(261) 120.21(17) C(265)-C(266)-H(266) 119.9 C(261)-C(266)-H(266) 119.9 C(3)-Ru(1)-C(2) 89.82(6) C(3)-Ru(1)-C(4) 90.89(6) C(2)-Ru(1)-C(4) 95.16(6) C(3)-Ru(1)-C(1) 91.81(6) C(2)-Ru(1)-C(1) 91.23(6) C(4)-Ru(1)-C(1) 173.07(6) C(3)-Ru(1)-N(6) 173.07(5) 154 C(2)-Ru(1)-N(6) 97.09(6) C(4)-Ru(1)-N(6) 87.97(6) C(1)-Ru(1)-N(6) 88.57(6) C(3)-Ru(1)-N(5) 95.39(6) C(2)-Ru(1)-N(5) 173.98(5) C(4)-Ru(1)-N(5) 87.79(6) C(1)-Ru(1)-N(5) 85.60(6) N(6)-Ru(1)-N(5) 77.74(5) N(1)-C(1)-Ru(1) 170.03(13) C(1)-N(1)-B(1) 178.37(15) N(1)-B(1)-C(31) 102.99(12) N(1)-B(1)-C(11) 106.78(12) C(31)-B(1)-C(11) 114.19(13) N(1)-B(1)-C(21) 109.46(13) C(31)-B(1)-C(21) 116.03(13) C(11)-B(1)-C(21) 106.93(12) C(12)-C(11)-C(16) 113.69(14) C(12)-C(11)-B(1) 120.88(14) C(16)-C(11)-B(1) 125.36(14) F(12)-C(12)-C(13) 115.56(14) F(12)-C(12)-C(11) 119.88(14) C(13)-C(12)-C(11) 124.55(15) F(13)-C(13)-C(14) 119.89(15) F(13)-C(13)-C(12) 121.08(16) 155 C(14)-C(13)-C(12) 119.02(15) F(14)-C(14)-C(15) 120.79(16) F(14)-C(14)-C(13) 119.86(16) C(15)-C(14)-C(13) 119.34(15) F(15)-C(15)-C(14) 119.71(15) F(15)-C(15)-C(16) 120.67(15) C(14)-C(15)-C(16) 119.59(15) F(16)-C(16)-C(15) 115.76(14) F(16)-C(16)-C(11) 120.55(14) C(15)-C(16)-C(11) 123.68(15) C(26)-C(21)-C(22) 113.12(15) C(26)-C(21)-B(1) 126.92(14) C(22)-C(21)-B(1) 119.87(14) F(22)-C(22)-C(23) 115.97(15) F(22)-C(22)-C(21) 119.40(15) C(23)-C(22)-C(21) 124.62(17) F(23)-C(23)-C(24) 120.04(17) F(23)-C(23)-C(22) 120.39(19) C(24)-C(23)-C(22) 119.58(17) F(24)-C(24)-C(25) 120.98(19) F(24)-C(24)-C(23) 120.39(19) C(25)-C(24)-C(23) 118.63(16) F(25)-C(25)-C(24) 120.01(17) F(25)-C(25)-C(26) 119.97(18) 156 C(24)-C(25)-C(26) 120.02(17) F(26)-C(26)-C(21) 121.21(15) F(26)-C(26)-C(25) 114.77(16) C(21)-C(26)-C(25) 124.01(16) C(32)-C(31)-C(36) 113.95(14) C(32)-C(31)-B(1) 125.82(14) C(36)-C(31)-B(1) 119.75(13) F(32)-C(32)-C(33) 115.56(14) F(32)-C(32)-C(31) 120.42(14) C(33)-C(32)-C(31) 124.02(15) F(33)-C(33)-C(34) 119.99(16) F(33)-C(33)-C(32) 120.75(16) C(34)-C(33)-C(32) 119.26(16) F(34)-C(34)-C(33) 119.91(17) F(34)-C(34)-C(35) 120.60(17) C(33)-C(34)-C(35) 119.49(16) F(35)-C(35)-C(34) 119.82(16) F(35)-C(35)-C(36) 120.95(16) C(34)-C(35)-C(36) 119.24(16) F(36)-C(36)-C(35) 116.39(15) F(36)-C(36)-C(31) 119.59(14) C(35)-C(36)-C(31) 124.01(15) N(2)-C(2)-Ru(1) 176.87(13) C(2)-N(2)-B(2) 171.18(14) 157 N(2)-B(2)-C(51) 108.03(12) N(2)-B(2)-C(61) 104.28(12) C(51)-B(2)-C(61) 109.69(12) N(2)-B(2)-C(41) 107.00(12) C(51)-B(2)-C(41) 112.71(12) C(61)-B(2)-C(41) 114.55(12) C(46)-C(41)-C(42) 113.96(13) C(46)-C(41)-B(2) 125.04(13) C(42)-C(41)-B(2) 121.00(13) F(42)-C(42)-C(43) 116.20(14) F(42)-C(42)-C(41) 119.79(13) C(43)-C(42)-C(41) 124.00(14) F(43)-C(43)-C(44) 119.42(14) F(43)-C(43)-C(42) 120.99(15) C(44)-C(43)-C(42) 119.60(14) F(44)-C(44)-C(45) 120.26(15) F(44)-C(44)-C(43) 120.71(15) C(45)-C(44)-C(43) 119.03(14) F(45)-C(45)-C(44) 119.66(13) F(45)-C(45)-C(46) 120.56(14) C(44)-C(45)-C(46) 119.77(14) F(46)-C(46)-C(45) 115.10(13) F(46)-C(46)-C(41) 121.27(13) C(45)-C(46)-C(41) 123.62(14) 158 C(52)-C(51)-C(56) 113.64(15) C(52)-C(51)-B(2) 122.03(14) C(56)-C(51)-B(2) 124.32(14) F(52)-C(52)-C(53) 116.23(16) F(52)-C(52)-C(51) 119.84(14) C(53)-C(52)-C(51) 123.88(17) F(53)-C(53)-C(54) 120.45(17) F(53)-C(53)-C(52) 120.03(19) C(54)-C(53)-C(52) 119.50(18) F(54)-C(54)-C(55) 120.4(2) F(54)-C(54)-C(53) 120.2(2) C(55)-C(54)-C(53) 119.38(17) F(55)-C(55)-C(54) 119.72(18) F(55)-C(55)-C(56) 120.6(2) C(54)-C(55)-C(56) 119.64(18) F(56)-C(56)-C(55) 114.93(16) F(56)-C(56)-C(51) 121.15(15) C(55)-C(56)-C(51) 123.93(18) C(66)-C(61)-C(62) 114.07(14) C(66)-C(61)-B(2) 126.81(13) C(62)-C(61)-B(2) 119.05(14) F(62)-C(62)-C(63) 115.98(15) F(62)-C(62)-C(61) 119.90(14) C(63)-C(62)-C(61) 124.10(17) 159 F(63)-C(63)-C(64) 120.14(16) F(63)-C(63)-C(62) 120.59(18) C(64)-C(63)-C(62) 119.27(17) F(64)-C(64)-C(65) 120.4(2) F(64)-C(64)-C(63) 120.30(19) C(65)-C(64)-C(63) 119.33(16) F(65)-C(65)-C(64) 120.30(16) F(65)-C(65)-C(66) 120.03(17) C(64)-C(65)-C(66) 119.67(18) F(66)-C(66)-C(61) 121.12(14) F(66)-C(66)-C(65) 115.31(15) C(61)-C(66)-C(65) 123.56(16) N(3)-C(3)-Ru(1) 175.87(13) C(3)-N(3)-B(3) 175.27(14) N(3)-B(3)-C(91) 104.58(12) N(3)-B(3)-C(71) 105.47(15) C(91)-B(3)-C(71) 115.06(15) N(3)-B(3)-C(71A) 114.3(4) C(91)-B(3)-C(71A) 109.1(4) N(3)-B(3)-C(81) 107.77(12) C(91)-B(3)-C(81) 114.15(12) C(71)-B(3)-C(81) 109.10(14) C(71A)-B(3)-C(81) 107.1(3) C(76)-C(71)-C(72) 113.7(2) 160 C(76)-C(71)-B(3) 125.9(2) C(72)-C(71)-B(3) 120.0(2) F(72)-C(72)-C(73) 116.1(2) F(72)-C(72)-C(71) 120.2(2) C(73)-C(72)-C(71) 123.6(3) F(73)-C(73)-C(74) 119.7(2) F(73)-C(73)-C(72) 120.5(3) C(74)-C(73)-C(72) 119.8(2) F(74)-C(74)-C(75) 120.5(3) F(74)-C(74)-C(73) 120.1(3) C(75)-C(74)-C(73) 119.3(2) F(75)-C(75)-C(74) 120.9(3) F(75)-C(75)-C(76) 119.9(3) C(74)-C(75)-C(76) 119.2(2) F(76)-C(76)-C(71) 120.3(2) F(76)-C(76)-C(75) 115.4(2) C(71)-C(76)-C(75) 124.3(3) C(72A)-C(71A)-C(76A) 114.7(10) C(72A)-C(71A)-B(3) 121.9(9) C(76A)-C(71A)-B(3) 123.3(9) F(72A)-C(72A)-C(71A) 120.0(11) F(72A)-C(72A)-C(73A) 115.3(10) C(71A)-C(72A)-C(73A) 124.6(10) F(73A)-C(73A)-C(74A) 123.0(10) 161 F(73A)-C(73A)-C(72A) 120.0(10) C(74A)-C(73A)-C(72A) 117.0(9) C(73A)-C(74A)-C(75A) 121.8(9) C(73A)-C(74A)-F(74A) 119.2(10) C(75A)-C(74A)-F(74A) 119.0(10) C(74A)-C(75A)-F(75A) 121.8(9) C(74A)-C(75A)-C(76A) 119.8(9) F(75A)-C(75A)-C(76A) 118.4(9) F(76A)-C(76A)-C(71A) 120.6(9) F(76A)-C(76A)-C(75A) 117.2(9) C(71A)-C(76A)-C(75A) 121.9(10) C(82)-C(81)-C(86) 113.42(14) C(82)-C(81)-B(3) 124.96(13) C(86)-C(81)-B(3) 121.61(13) F(82)-C(82)-C(83) 114.76(13) F(82)-C(82)-C(81) 121.16(14) C(83)-C(82)-C(81) 124.08(15) F(83)-C(83)-C(84) 120.11(14) F(83)-C(83)-C(82) 120.05(15) C(84)-C(83)-C(82) 119.84(14) F(84)-C(84)-C(83) 120.94(15) F(84)-C(84)-C(85) 120.31(16) C(83)-C(84)-C(85) 118.75(14) F(85)-C(85)-C(84) 119.69(14) 162 F(85)-C(85)-C(86) 120.65(14) C(84)-C(85)-C(86) 119.65(15) F(86)-C(86)-C(85) 115.79(14) F(86)-C(86)-C(81) 120.00(13) C(85)-C(86)-C(81) 124.19(14) C(92)-C(91)-C(96) 113.74(13) C(92)-C(91)-B(3) 127.37(13) C(96)-C(91)-B(3) 118.83(13) F(92)-C(92)-C(91) 120.79(14) F(92)-C(92)-C(93) 115.95(14) C(91)-C(92)-C(93) 123.26(15) F(93)-C(93)-C(94) 119.36(14) F(93)-C(93)-C(92) 120.43(15) C(94)-C(93)-C(92) 120.21(15) F(94)-C(94)-C(93) 120.54(15) F(94)-C(94)-C(95) 120.51(15) C(93)-C(94)-C(95) 118.95(14) F(95)-C(95)-C(94) 120.36(13) F(95)-C(95)-C(96) 120.49(14) C(94)-C(95)-C(96) 119.14(14) F(96)-C(96)-C(95) 116.13(13) F(96)-C(96)-C(91) 119.18(13) C(95)-C(96)-C(91) 124.68(14) N(4)-C(4)-Ru(1) 169.58(13) 163 C(4)-N(4)-B(4) 174.77(15) N(4)-B(4)-C(01B) 102.8(4) N(4)-B(4)-C(121) 105.41(13) C(01B)-B(4)-C(121) 120.6(2) N(4)-B(4)-C(111) 104.52(12) C(01B)-B(4)-C(111) 107.0(3) C(121)-B(4)-C(111) 114.61(14) N(4)-B(4)-C(101) 110.2(2) C(121)-B(4)-C(101) 115.49(17) C(111)-B(4)-C(101) 106.10(19) C(102)-C(101)-C(106) 113.2(4) C(102)-C(101)-B(4) 121.0(4) C(106)-C(101)-B(4) 125.5(4) F(102)-C(102)-C(103) 116.8(3) F(102)-C(102)-C(101) 119.2(3) C(103)-C(102)-C(101) 124.0(4) F(103)-C(103)-C(104) 119.8(3) F(103)-C(103)-C(102) 120.3(4) C(104)-C(103)-C(102) 119.9(3) F(104)-C(104)-C(105) 120.2(4) F(104)-C(104)-C(103) 120.6(4) C(105)-C(104)-C(103) 119.1(4) F(105)-C(105)-C(104) 120.9(4) F(105)-C(105)-C(106) 119.8(5) 164 C(104)-C(105)-C(106) 119.3(4) F(106)-C(106)-C(101) 121.4(5) F(106)-C(106)-C(105) 114.4(4) C(101)-C(106)-C(105) 124.2(5) C(06B)-C(01B)-C(02B) 113.4(8) C(06B)-C(01B)-B(4) 126.2(8) C(02B)-C(01B)-B(4) 120.4(7) F(02B)-C(02B)-C(03B) 116.3(6) F(02B)-C(02B)-C(01B) 120.8(7) C(03B)-C(02B)-C(01B) 122.9(7) F(03B)-C(03B)-C(04B) 121.5(7) F(03B)-C(03B)-C(02B) 119.5(7) C(04B)-C(03B)-C(02B) 119.0(6) C(03B)-C(04B)-F(04B) 118.7(8) C(03B)-C(04B)-C(05B) 119.1(8) F(04B)-C(04B)-C(05B) 122.1(8) F(05B)-C(05B)-C(04B) 118.9(8) F(05B)-C(05B)-C(06B) 119.9(8) C(04B)-C(05B)-C(06B) 121.1(9) F(06B)-C(06B)-C(05B) 117.5(8) F(06B)-C(06B)-C(01B) 118.4(8) C(05B)-C(06B)-C(01B) 124.0(9) C(116)-C(111)-C(112) 114.04(16) C(116)-C(111)-B(4) 126.00(16) 165 C(112)-C(111)-B(4) 119.89(15) F(112)-C(112)-C(113) 115.80(16) F(112)-C(112)-C(111) 119.80(15) C(113)-C(112)-C(111) 124.39(18) F(113)-C(113)-C(114) 120.41(17) F(113)-C(113)-C(112) 120.65(18) C(114)-C(113)-C(112) 118.94(18) F(114)-C(114)-C(115) 119.94(19) F(114)-C(114)-C(113) 120.46(19) C(115)-C(114)-C(113) 119.60(17) F(115)-C(115)-C(114) 120.01(17) F(115)-C(115)-C(116) 120.36(19) C(114)-C(115)-C(116) 119.62(18) F(116)-C(116)-C(111) 120.92(16) F(116)-C(116)-C(115) 115.69(17) C(111)-C(116)-C(115) 123.39(18) C(126)-C(121)-C(122) 113.71(15) C(126)-C(121)-B(4) 126.08(14) C(122)-C(121)-B(4) 120.16(14) F(122)-C(122)-C(123) 116.36(14) F(122)-C(122)-C(121) 119.46(15) C(123)-C(122)-C(121) 124.16(15) F(123)-C(123)-C(122) 121.33(15) F(123)-C(123)-C(124) 119.25(16) 166 C(122)-C(123)-C(124) 119.42(15) F(124)-C(124)-C(125) 121.22(16) F(124)-C(124)-C(123) 119.99(16) C(125)-C(124)-C(123) 118.78(16) F(125)-C(125)-C(124) 119.53(17) F(125)-C(125)-C(126) 120.54(17) C(124)-C(125)-C(126) 119.93(16) F(126)-C(126)-C(125) 115.69(15) F(126)-C(126)-C(121) 120.33(16) C(125)-C(126)-C(121) 123.98(16) C(131)-N(5)-C(135) 119.33(13) C(131)-N(5)-Ru(1) 125.08(10) C(135)-N(5)-Ru(1) 115.28(10) N(5)-C(131)-C(132) 122.61(15) N(5)-C(131)-H(131) 118.7 C(132)-C(131)-H(131) 118.7 C(133)-C(132)-C(131) 117.97(15) C(133)-C(132)-H(132) 121.0 C(131)-C(132)-H(132) 121.0 C(134)-C(133)-C(132) 120.04(14) C(134)-C(133)-C(141) 120.95(15) C(132)-C(133)-C(141) 118.97(15) F(131)-C(141)-F(132) 111.0(9) F(33B)-C(141)-F(32B) 104.5(9) 167 F(33B)-C(141)-F(31B) 109.4(8) F(32B)-C(141)-F(31B) 102.6(9) F(131)-C(141)-F(133) 104.4(9) F(132)-C(141)-F(133) 108.5(7) F(131)-C(141)-C(133) 111.7(6) F(33B)-C(141)-C(133) 116.7(9) F(132)-C(141)-C(133) 113.1(5) F(32B)-C(141)-C(133) 111.9(7) F(31B)-C(141)-C(133) 110.7(7) F(133)-C(141)-C(133) 107.7(8) C(133)-C(134)-C(135) 118.96(14) C(133)-C(134)-H(134) 120.5 C(135)-C(134)-H(134) 120.5 N(5)-C(135)-C(134) 120.94(14) N(5)-C(135)-C(136) 115.63(13) C(134)-C(135)-C(136) 123.39(14) N(6)-C(136)-C(137) 121.34(14) N(6)-C(136)-C(135) 115.23(13) C(137)-C(136)-C(135) 123.43(14) C(138)-C(137)-C(136) 119.03(15) C(138)-C(137)-H(137) 120.5 C(136)-C(137)-H(137) 120.5 C(137)-C(138)-C(139) 119.70(15) C(137)-C(138)-C(142) 120.70(16) 168 C(139)-C(138)-C(142) 119.59(17) F(34B)-C(142)-F(36B) 113.8(7) F(34B)-C(142)-F(35B) 109.6(10) F(36B)-C(142)-F(35B) 101.9(8) F(135)-C(142)-F(136) 109.4(5) F(135)-C(142)-F(134) 105.3(7) F(136)-C(142)-F(134) 102.9(4) F(34B)-C(142)-C(138) 113.8(6) F(135)-C(142)-C(138) 115.1(5) F(36B)-C(142)-C(138) 109.2(4) F(35B)-C(142)-C(138) 107.8(7) F(136)-C(142)-C(138) 113.0(3) F(134)-C(142)-C(138) 110.3(4) C(140)-C(139)-C(138) 118.56(16) C(140)-C(139)-H(139) 120.7 C(138)-C(139)-H(139) 120.7 N(6)-C(140)-C(139) 122.45(15) N(6)-C(140)-H(140) 118.8 C(139)-C(140)-H(140) 118.8 C(140)-N(6)-C(136) 118.91(13) C(140)-N(6)-Ru(1) 125.46(10) C(136)-N(6)-Ru(1) 115.64(10) C(11S)-O(1S)-H(1S) 109.5 O(1S)-C(11S)-C(12S) 109.5(16) 169 O(1S)-C(11S)-H(11A) 109.8 C(12S)-C(11S)-H(11A) 109.8 O(1S)-C(11S)-H(11B) 109.8 C(12S)-C(11S)-H(11B) 109.8 H(11A)-C(11S)-H(11B) 108.2 C(11S)-C(12S)-H(12A) 109.5 C(11S)-C(12S)-H(12B) 109.5 H(12A)-C(12S)-H(12B) 109.5 C(11S)-C(12S)-H(12C) 109.5 H(12A)-C(12S)-H(12C) 109.5 H(12B)-C(12S)-H(12C) 109.5 C(21S)-O(2S)-H(2S) 109.5 O(2S)-C(21S)-C(22S) 108.2(16) O(2S)-C(21S)-H(21A) 110.1 C(22S)-C(21S)-H(21A) 110.1 O(2S)-C(21S)-H(21B) 110.1 C(22S)-C(21S)-H(21B) 110.1 H(21A)-C(21S)-H(21B) 108.4 C(21S)-C(22S)-H(22A) 109.5 C(21S)-C(22S)-H(22B) 109.5 H(22A)-C(22S)-H(22B) 109.5 C(21S)-C(22S)-H(22C) 109.5 H(22A)-C(22S)-H(22C) 109.5 H(22B)-C(22S)-H(22C) 109.5 170 C(31S)-O(3S)-H(3S) 109.5 O(3S)-C(31S)-C(32S) 111.4(19) O(3S)-C(31S)-H(31A) 109.4 C(32S)-C(31S)-H(31A) 109.4 O(3S)-C(31S)-H(31B) 109.4 C(32S)-C(31S)-H(31B) 109.4 H(31A)-C(31S)-H(31B) 108.0 C(31S)-C(32S)-H(32A) 109.5 C(31S)-C(32S)-H(32B) 109.5 H(32A)-C(32S)-H(32B) 109.5 C(31S)-C(32S)-H(32C) 109.5 H(32A)-C(32S)-H(32C) 109.5 H(32B)-C(32S)-H(32C) 109.5 _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: 171 Table 4. Anisotropic displacement parameters (Å2x 103) for D19108. The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ N(7) 21(1) 19(1) 22(1) -7(1) 2(1) -8(1) P(1) 22(1) 24(1) 21(1) -6(1) 0(1) -10(1) C(151) 18(2) 33(2) 40(2) -5(2) -1(2) -13(1) C(152) 28(2) 46(2) 70(3) 9(2) -6(2) -17(2) C(153) 26(2) 73(3) 106(4) 15(3) -9(2) -25(2) C(154) 30(2) 68(3) 116(4) 2(3) -23(2) -8(2) C(155) 33(2) 71(3) 46(2) -1(2) -13(2) -13(2) C(156) 24(2) 43(2) 28(2) -6(1) -4(1) -10(1) C(51B) 39(5) 44(5) 31(5) 3(4) -13(4) -16(3) C(52B) 32(3) 44(4) 57(5) 4(3) -18(3) -19(3) C(53B) 28(3) 51(4) 66(5) 3(4) -14(3) -20(3) C(54B) 28(4) 65(6) 106(6) 1(6) -39(4) -17(4) C(55B) 34(4) 40(4) 105(7) -13(5) -30(5) 3(3) C(56B) 34(4) 30(3) 78(6) -11(4) -19(5) -12(3) C(161) 28(1) 26(1) 22(1) -7(1) 3(1) -15(1) C(162) 34(1) 44(1) 31(1) -9(1) 10(1) -10(1) C(163) 42(1) 56(1) 31(1) -18(1) 15(1) -21(1) C(164) 50(1) 61(1) 21(1) -13(1) 3(1) -36(1) C(165) 53(1) 51(1) 26(1) -8(1) -12(1) -12(1) 172 C(166) 40(1) 38(1) 24(1) -11(1) -4(1) -5(1) C(171) 38(1) 23(1) 22(1) -7(1) -6(1) -11(1) C(172) 109(2) 37(1) 36(1) -18(1) 16(1) -41(1) C(173) 142(3) 32(1) 47(1) -19(1) 9(2) -39(2) C(174) 83(2) 28(1) 39(1) -18(1) -17(1) 0(1) C(175) 36(1) 32(1) 30(1) -12(1) -13(1) 6(1) C(176) 25(1) 24(1) 28(1) -6(1) -9(1) -1(1) P(2) 13(1) 17(1) 15(1) -5(1) 0(1) -3(1) C(181) 15(1) 20(1) 14(1) -6(1) -1(1) -2(1) C(182) 22(1) 20(1) 26(1) -7(1) -7(1) -1(1) C(183) 26(1) 30(1) 38(1) -13(1) -16(1) 6(1) C(184) 20(1) 40(1) 31(1) -13(1) -10(1) -4(1) C(185) 26(1) 28(1) 30(1) -6(1) -8(1) -10(1) C(186) 22(1) 20(1) 26(1) -4(1) -7(1) -4(1) C(191) 13(1) 24(1) 17(1) -4(1) -1(1) -4(1) C(192) 19(1) 30(1) 21(1) -9(1) -2(1) -3(1) C(193) 22(1) 44(1) 16(1) -9(1) -2(1) -5(1) C(194) 21(1) 42(1) 19(1) 4(1) -4(1) -6(1) C(195) 24(1) 25(1) 28(1) 1(1) -6(1) -4(1) C(196) 20(1) 23(1) 21(1) -4(1) -4(1) -4(1) C(201) 16(1) 21(1) 17(1) -6(1) 2(1) -3(1) C(202) 19(1) 36(1) 22(1) -3(1) 0(1) 2(1) C(203) 22(1) 42(1) 32(1) -6(1) 6(1) 6(1) C(204) 30(1) 36(1) 27(1) -12(1) 12(1) -5(1) 173 C(205) 32(1) 44(1) 20(1) -14(1) 2(1) -10(1) C(206) 21(1) 36(1) 21(1) -10(1) -2(1) -4(1) N(8) 20(1) 37(1) 27(1) -3(1) -5(1) 5(1) P(3) 12(1) 35(1) 21(1) -5(1) -3(1) -2(1) C(211) 15(1) 24(1) 39(1) -7(1) -8(1) -1(1) C(212) 28(1) 57(1) 56(1) -29(1) -21(1) 9(1) C(213) 41(1) 43(1) 79(2) -24(1) -40(1) 6(1) C(214) 20(1) 23(1) 86(2) 4(1) -23(1) -3(1) C(215) 15(1) 41(1) 59(1) 13(1) -4(1) 0(1) C(216) 16(1) 24(1) 39(1) 5(1) -3(1) -1(1) C(221) 18(1) 38(1) 18(1) -7(1) -1(1) -6(1) C(222) 22(1) 66(2) 34(1) 11(1) -11(1) -10(1) C(223) 32(1) 69(2) 38(1) 19(1) -12(1) -14(1) C(224) 30(1) 52(1) 27(1) 1(1) -2(1) -15(1) C(225) 22(1) 40(1) 32(1) -11(1) -2(1) -8(1) C(226) 20(1) 32(1) 28(1) -9(1) -6(1) -3(1) C(231) 13(1) 53(1) 21(1) -7(1) 0(1) -9(1) C(232) 18(1) 57(1) 25(1) -14(1) 0(1) -6(1) C(233) 24(1) 77(2) 32(1) -25(1) 2(1) -12(1) C(234) 30(1) 101(2) 23(1) -19(1) 4(1) -24(1) C(235) 30(1) 88(2) 22(1) 4(1) -1(1) -25(1) C(236) 23(1) 64(1) 26(1) -1(1) -1(1) -17(1) P(4) 15(1) 27(1) 26(1) 0(1) -6(1) -1(1) C(241) 17(1) 27(1) 31(1) -4(1) -8(1) -1(1) 174 C(242) 21(1) 52(1) 24(1) -1(1) -4(1) 6(1) C(243) 26(1) 57(1) 28(1) 1(1) -10(1) 5(1) C(244) 21(1) 33(1) 49(1) -5(1) -14(1) 3(1) C(245) 25(1) 42(1) 57(1) -29(1) -16(1) 9(1) C(246) 25(1) 41(1) 43(1) -21(1) -15(1) 4(1) C(251) 22(1) 29(1) 35(1) 10(1) -14(1) -6(1) C(252) 33(1) 31(1) 48(1) 3(1) -17(1) -7(1) C(253) 52(1) 30(1) 60(1) 7(1) -30(1) -13(1) C(254) 39(1) 42(1) 63(2) 24(1) -31(1) -19(1) C(255) 27(1) 50(1) 58(1) 17(1) -15(1) -14(1) C(256) 25(1) 43(1) 45(1) 9(1) -10(1) -7(1) C(261) 19(1) 24(1) 24(1) -4(1) -5(1) -2(1) C(262) 24(1) 29(1) 33(1) 2(1) -12(1) -9(1) C(263) 35(1) 40(1) 32(1) 2(1) -17(1) -14(1) C(264) 37(1) 42(1) 27(1) 1(1) -8(1) -15(1) C(265) 29(1) 48(1) 29(1) -5(1) -4(1) -19(1) C(266) 24(1) 40(1) 26(1) -9(1) -5(1) -11(1) Ru(1) 10(1) 12(1) 16(1) -3(1) -4(1) -2(1) C(1) 12(1) 16(1) 20(1) -1(1) -6(1) -4(1) N(1) 15(1) 16(1) 21(1) -4(1) -4(1) -2(1) B(1) 15(1) 16(1) 20(1) -6(1) -3(1) 1(1) C(11) 16(1) 17(1) 21(1) -6(1) -5(1) 2(1) C(12) 22(1) 19(1) 24(1) -7(1) -7(1) 3(1) F(12) 41(1) 24(1) 23(1) -9(1) -12(1) 2(1) 175 C(13) 26(1) 25(1) 22(1) -1(1) -7(1) 3(1) F(13) 46(1) 32(1) 21(1) 1(1) -8(1) 2(1) C(14) 26(1) 16(1) 33(1) 3(1) -8(1) -1(1) F(14) 49(1) 19(1) 38(1) 6(1) -12(1) -5(1) C(15) 25(1) 17(1) 33(1) -8(1) -10(1) 0(1) F(15) 49(1) 18(1) 42(1) -10(1) -15(1) -4(1) C(16) 20(1) 19(1) 22(1) -6(1) -6(1) 0(1) F(16) 38(1) 21(1) 22(1) -8(1) -9(1) -3(1) C(21) 16(1) 23(1) 19(1) -4(1) -4(1) -2(1) C(22) 19(1) 31(1) 26(1) -9(1) -5(1) 1(1) F(22) 25(1) 40(1) 48(1) -28(1) -4(1) 5(1) C(23) 18(1) 46(1) 30(1) -7(1) -5(1) 6(1) F(23) 22(1) 70(1) 69(1) -29(1) -9(1) 18(1) C(24) 16(1) 58(1) 27(1) -2(1) -7(1) -9(1) F(24) 18(1) 90(1) 50(1) -10(1) -13(1) -12(1) C(25) 26(1) 44(1) 26(1) -6(1) -4(1) -19(1) F(25) 39(1) 63(1) 52(1) -18(1) -6(1) -31(1) C(26) 21(1) 28(1) 28(1) -8(1) -1(1) -7(1) F(26) 28(1) 33(1) 66(1) -27(1) -1(1) -10(1) C(31) 17(1) 15(1) 21(1) -5(1) -5(1) 1(1) C(32) 18(1) 22(1) 24(1) -4(1) -6(1) -2(1) F(32) 18(1) 50(1) 25(1) -1(1) -3(1) -12(1) C(33) 30(1) 26(1) 22(1) -1(1) -4(1) -4(1) F(33) 41(1) 50(1) 22(1) 6(1) -6(1) -15(1) 176 C(34) 31(1) 34(1) 27(1) -2(1) -16(1) 4(1) F(34) 44(1) 62(1) 34(1) 3(1) -25(1) 4(1) C(35) 17(1) 40(1) 34(1) -10(1) -11(1) 3(1) F(35) 19(1) 82(1) 44(1) -16(1) -15(1) 1(1) C(36) 17(1) 25(1) 24(1) -7(1) -3(1) 0(1) F(36) 18(1) 45(1) 28(1) -8(1) -2(1) -9(1) C(2) 14(1) 14(1) 16(1) -5(1) 0(1) -2(1) N(2) 13(1) 18(1) 19(1) -6(1) -2(1) -2(1) B(2) 11(1) 19(1) 18(1) -6(1) -4(1) -2(1) C(41) 13(1) 16(1) 15(1) -3(1) -4(1) -2(1) C(42) 15(1) 19(1) 22(1) -6(1) -5(1) -2(1) F(42) 19(1) 29(1) 41(1) -18(1) -5(1) -7(1) C(43) 24(1) 21(1) 20(1) -10(1) -8(1) 3(1) F(43) 32(1) 34(1) 36(1) -25(1) -9(1) 3(1) C(44) 17(1) 25(1) 17(1) -5(1) -2(1) 6(1) F(44) 20(1) 38(1) 25(1) -12(1) 1(1) 7(1) C(45) 11(1) 26(1) 21(1) -3(1) -3(1) -3(1) F(45) 12(1) 46(1) 42(1) -17(1) 1(1) -8(1) C(46) 14(1) 18(1) 19(1) -5(1) -5(1) -2(1) F(46) 15(1) 31(1) 32(1) -16(1) -5(1) -5(1) C(51) 10(1) 23(1) 27(1) -12(1) -2(1) -2(1) C(52) 17(1) 22(1) 36(1) -11(1) -8(1) -1(1) F(52) 42(1) 26(1) 34(1) 0(1) -13(1) -12(1) C(53) 28(1) 19(1) 63(1) -14(1) -15(1) 2(1) 177 F(53) 64(1) 18(1) 90(1) -8(1) -36(1) 0(1) C(54) 32(1) 31(1) 71(2) -34(1) -16(1) 2(1) F(54) 72(1) 39(1) 109(1) -50(1) -38(1) 5(1) C(55) 32(1) 45(1) 46(1) -29(1) -14(1) -3(1) F(55) 74(1) 69(1) 58(1) -39(1) -30(1) -12(1) C(56) 22(1) 31(1) 33(1) -15(1) -8(1) -5(1) F(56) 59(1) 42(1) 35(1) -7(1) -27(1) -16(1) C(61) 16(1) 24(1) 16(1) -8(1) -3(1) -7(1) C(62) 19(1) 32(1) 20(1) -11(1) -1(1) -9(1) F(62) 19(1) 36(1) 34(1) -17(1) 2(1) -2(1) C(63) 27(1) 52(1) 19(1) -14(1) 3(1) -19(1) F(63) 32(1) 77(1) 28(1) -22(1) 14(1) -24(1) C(64) 44(1) 51(1) 14(1) 0(1) -2(1) -27(1) F(64) 67(1) 70(1) 19(1) 7(1) 1(1) -36(1) C(65) 40(1) 33(1) 21(1) 3(1) -14(1) -13(1) F(65) 59(1) 38(1) 35(1) 15(1) -21(1) -10(1) C(66) 20(1) 28(1) 18(1) -5(1) -7(1) -7(1) F(66) 21(1) 24(1) 27(1) -2(1) -9(1) 0(1) C(3) 11(1) 16(1) 19(1) -7(1) -6(1) 1(1) N(3) 14(1) 16(1) 22(1) -4(1) -6(1) -1(1) B(3) 13(1) 15(1) 18(1) -4(1) -4(1) -3(1) C(71) 13(1) 21(1) 18(1) -6(1) -2(1) -9(1) C(72) 18(1) 25(1) 28(1) -12(1) -1(1) -6(1) F(72) 26(1) 21(1) 40(1) -8(1) 0(1) 4(1) 178 C(73) 17(1) 47(2) 41(2) -29(1) 2(1) -8(1) F(73) 28(1) 59(1) 68(2) -50(1) 4(1) -2(1) C(74) 20(1) 70(2) 28(1) -29(2) 0(1) -12(1) F(74) 31(1) 125(2) 34(1) -50(1) 3(1) -16(1) C(75) 20(1) 59(2) 20(1) -8(1) -6(1) -13(1) F(75) 30(1) 92(2) 18(1) -1(1) -7(1) -13(1) C(76) 15(1) 31(1) 23(1) -7(1) -4(1) -6(1) F(76) 30(1) 33(1) 22(1) 3(1) -5(1) 3(1) C(71A) 18(5) 30(5) 27(4) -12(4) 1(4) -5(4) C(72A) 31(5) 29(5) 27(4) -4(4) 0(4) -13(4) F(72A) 42(6) 31(5) 37(6) -11(4) 7(4) 1(4) C(73A) 27(5) 45(5) 29(4) -23(4) 4(4) -10(4) F(73A) 66(7) 59(6) 66(7) -48(5) 24(5) -18(5) C(74A) 21(5) 61(5) 24(4) -17(4) 3(4) -19(4) F(74A) 66(7) 111(9) 27(4) -34(5) 15(4) -56(6) C(75A) 16(4) 53(5) 22(4) -8(4) 1(3) -19(4) F(75A) 41(4) 84(7) 17(3) 12(4) -5(3) -15(5) C(76A) 17(4) 37(5) 14(3) -4(4) -2(3) -12(5) F(76A) 43(5) 36(5) 23(4) 5(3) 2(3) 10(4) C(81) 14(1) 13(1) 21(1) -4(1) -4(1) -1(1) C(82) 18(1) 19(1) 21(1) -5(1) -5(1) -3(1) F(82) 25(1) 38(1) 21(1) -4(1) -2(1) -16(1) C(83) 14(1) 21(1) 31(1) -6(1) -2(1) -4(1) F(83) 16(1) 42(1) 37(1) -9(1) 2(1) -14(1) 179 C(84) 14(1) 22(1) 38(1) -6(1) -13(1) -2(1) F(84) 20(1) 38(1) 49(1) -3(1) -20(1) -9(1) C(85) 23(1) 18(1) 26(1) -2(1) -12(1) -3(1) F(85) 34(1) 34(1) 27(1) 1(1) -18(1) -11(1) C(86) 16(1) 14(1) 23(1) -3(1) -6(1) -3(1) F(86) 23(1) 29(1) 20(1) -3(1) -4(1) -11(1) C(91) 14(1) 16(1) 17(1) -3(1) -4(1) -2(1) C(92) 20(1) 21(1) 33(1) -10(1) -13(1) 0(1) F(92) 27(1) 27(1) 82(1) -29(1) -31(1) 5(1) C(93) 29(1) 20(1) 35(1) -16(1) -14(1) 5(1) F(93) 42(1) 35(1) 81(1) -40(1) -34(1) 16(1) C(94) 19(1) 23(1) 22(1) -6(1) -2(1) 6(1) F(94) 23(1) 31(1) 36(1) -13(1) -3(1) 10(1) C(95) 12(1) 23(1) 25(1) -4(1) -2(1) -3(1) F(95) 11(1) 32(1) 54(1) -12(1) -7(1) -2(1) C(96) 16(1) 17(1) 21(1) -6(1) -4(1) -3(1) F(96) 18(1) 25(1) 44(1) -17(1) -11(1) -2(1) C(4) 13(1) 18(1) 19(1) -2(1) -6(1) -3(1) N(4) 18(1) 23(1) 20(1) -6(1) -5(1) -4(1) B(4) 21(1) 27(1) 16(1) -7(1) -3(1) -7(1) C(101) 15(2) 26(2) 14(1) -4(1) 1(1) -4(1) C(102) 30(2) 43(2) 19(1) -6(1) -4(1) -16(2) F(102) 86(2) 54(2) 21(1) -13(1) -1(1) -40(2) C(103) 32(2) 63(2) 20(2) 1(1) -9(1) -23(2) 180 F(103) 91(3) 106(3) 21(1) 8(1) -25(1) -64(2) C(104) 31(2) 52(2) 24(2) 12(2) -3(2) -6(2) F(104) 45(1) 74(2) 42(2) 29(1) -6(1) 1(2) C(105) 47(4) 30(2) 32(3) 2(2) 6(2) -3(2) F(105) 128(4) 28(1) 49(2) 0(1) 29(2) -5(2) C(106) 38(4) 36(2) 19(2) -9(1) 4(2) -8(2) F(106) 117(4) 36(2) 23(1) -9(1) 6(2) -35(2) C(01B) 30(4) 45(4) 21(3) -10(3) -11(3) -14(3) C(02B) 22(3) 44(4) 22(3) -3(2) -4(3) -18(3) F(02B) 83(5) 66(4) 19(2) -4(2) -11(3) -46(4) C(03B) 24(3) 61(4) 21(3) 5(3) -14(2) -13(3) F(03B) 66(4) 103(5) 28(3) 19(3) -29(3) -50(4) C(04B) 19(3) 48(4) 29(4) 10(3) -6(3) -6(3) F(04B) 29(2) 65(4) 48(4) 33(3) -2(3) -7(3) C(05B) 29(4) 41(3) 29(4) -1(3) 1(3) -13(3) F(05B) 73(5) 34(3) 54(4) 5(2) 8(3) -26(3) C(06B) 22(4) 33(3) 20(4) 2(3) -4(3) -16(3) F(06B) 56(4) 44(4) 23(2) 1(2) -6(2) -40(3) C(111) 24(1) 35(1) 17(1) -8(1) -3(1) -11(1) C(112) 25(1) 37(1) 20(1) -6(1) -7(1) -10(1) F(112) 25(1) 36(1) 35(1) -10(1) -12(1) -2(1) C(113) 24(1) 49(1) 23(1) -5(1) -7(1) -12(1) F(113) 22(1) 61(1) 39(1) -7(1) -11(1) -9(1) C(114) 31(1) 54(1) 23(1) -2(1) -8(1) -26(1) 181 F(114) 39(1) 66(1) 37(1) -1(1) -12(1) -35(1) C(115) 42(1) 40(1) 26(1) -11(1) -5(1) -22(1) F(115) 56(1) 50(1) 49(1) -22(1) -5(1) -31(1) C(116) 30(1) 40(1) 26(1) -15(1) -1(1) -13(1) F(116) 35(1) 45(1) 60(1) -35(1) 1(1) -12(1) C(121) 22(1) 26(1) 16(1) -8(1) -2(1) -8(1) C(122) 24(1) 25(1) 18(1) -6(1) 2(1) -6(1) F(122) 37(1) 31(1) 26(1) -1(1) 10(1) 0(1) C(123) 31(1) 26(1) 20(1) -2(1) -4(1) -5(1) F(123) 46(1) 37(1) 28(1) 8(1) -1(1) 3(1) C(124) 21(1) 35(1) 30(1) -5(1) -6(1) -2(1) F(124) 24(1) 49(1) 44(1) -1(1) -7(1) 3(1) C(125) 19(1) 51(1) 26(1) -5(1) 3(1) -5(1) F(125) 26(1) 84(1) 39(1) 9(1) 13(1) 7(1) C(126) 25(1) 40(1) 16(1) 0(1) -1(1) -6(1) F(126) 35(1) 69(1) 19(1) 12(1) 5(1) 4(1) N(5) 14(1) 16(1) 20(1) -4(1) -6(1) -2(1) C(131) 17(1) 19(1) 28(1) -3(1) -8(1) -3(1) C(132) 15(1) 27(1) 29(1) -5(1) -9(1) -5(1) C(133) 17(1) 26(1) 23(1) -8(1) -10(1) 1(1) C(141) 20(1) 36(1) 31(1) -6(1) -13(1) 0(1) F(131) 24(2) 95(6) 38(3) -7(3) -6(2) 16(3) F(132) 26(4) 31(3) 32(3) -7(2) -14(3) 9(3) F(133) 35(3) 41(3) 63(3) 7(2) -39(2) -9(3) 182 F(31B) 20(3) 43(4) 37(3) -18(2) -13(2) 15(2) F(32B) 36(6) 36(5) 48(5) 3(4) -32(4) -4(4) F(33B) 22(2) 33(3) 40(3) -8(3) -25(3) 0(2) C(134) 21(1) 19(1) 21(1) -4(1) -10(1) 1(1) C(135) 16(1) 17(1) 19(1) -6(1) -6(1) -1(1) C(136) 17(1) 17(1) 20(1) -4(1) -6(1) -3(1) C(137) 27(1) 21(1) 23(1) 2(1) -10(1) -5(1) C(138) 34(1) 22(1) 28(1) 5(1) -10(1) -12(1) C(142) 47(1) 35(1) 51(1) 18(1) -19(1) -22(1) F(134) 134(5) 33(3) 100(4) 23(2) -74(4) -46(3) F(135) 82(4) 50(2) 60(3) 32(2) 18(3) -9(3) F(136) 52(2) 34(2) 64(3) 25(2) -26(2) -13(1) F(34B) 112(7) 23(2) 102(6) 8(3) 14(5) -13(4) F(35B) 64(4) 70(5) 69(5) 42(4) 2(3) -28(3) F(36B) 101(6) 88(7) 86(6) 67(5) -63(5) -58(5) C(139) 27(1) 29(1) 33(1) 2(1) -8(1) -16(1) C(140) 20(1) 24(1) 28(1) -1(1) -7(1) -8(1) N(6) 16(1) 17(1) 19(1) -3(1) -5(1) -4(1) O(1S) 205(17) 124(9) 175(16) -41(11) -7(15) -28(11) C(11S) 33(6) 100(8) 82(9) -55(7) 11(6) -31(7) C(12S) 104(13) 107(13) 59(10) -18(9) -8(9) -57(11) O(2S) 144(12) 113(11) 148(13) 23(10) 16(10) 36(10) C(21S) 71(12) 116(13) 110(15) -12(11) -37(10) 15(11) C(22S) 97(17) 138(19) 133(18) -36(16) -53(11) 8(18) 183 O(3S) 63(9) 102(9) 99(10) -46(8) 9(7) -31(8) C(31S) 69(10) 98(10) 94(11) -49(8) -1(9) -33(8) C(32S) 108(14) 86(13) 131(14) -52(11) 34(12) -23(12) ______________________________________________________________________________ 184 Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for D19108. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(152) 6553 7946 2425 62 H(153) 5172 8199 2185 90 H(154) 4886 9065 1360 90 H(155) 6039 9569 673 61 H(156) 7397 9378 947 38 H(52B) 6935 7555 2063 53 H(53B) 5516 7740 1886 59 H(54B) 5019 8759 1302 78 H(55B) 5704 9712 1182 71 H(56B) 7177 9494 1290 55 H(162) 7044 8794 2845 46 H(163) 6972 8497 3885 52 H(164) 7997 7689 4312 49 H(165) 9111 7166 3711 51 H(166) 9195 7458 2663 40 H(172) 7981 7037 2148 71 H(173) 8639 6147 1736 87 H(174) 9755 6295 901 58 185 H(175) 10235 7327 473 39 H(176) 9606 8217 894 30 H(182) 10290 8688 1876 27 H(183) 11698 8694 1988 36 H(184) 12209 9693 1850 34 H(185) 11308 10696 1620 32 H(186) 9896 10698 1511 27 H(192) 8970 9603 384 27 H(193) 8842 10358 -544 33 H(194) 8582 11492 -618 35 H(195) 8423 11884 234 33 H(196) 8531 11135 1170 26 H(202) 7172 10409 1694 33 H(203) 6188 10744 2487 44 H(204) 6558 10509 3433 40 H(205) 7911 9943 3591 38 H(206) 8920 9634 2793 31 H(212) 5664 2816 5237 53 H(213) 4213 2985 5137 59 H(214) 3119 3159 5942 54 H(215) 3460 3154 6844 54 H(216) 4904 2978 6955 36 H(222) 6028 3951 5279 54 H(223) 6800 4759 4560 62 186 H(224) 8284 4699 4499 46 H(225) 8987 3874 5187 37 H(226) 8232 3054 5889 32 H(232) 6635 3801 6695 40 H(233) 6628 3860 7673 51 H(234) 6528 2911 8470 60 H(235) 6482 1895 8301 59 H(236) 6516 1818 7322 47 H(242) 8126 1241 6696 43 H(243) 9418 625 6953 48 H(244) 10417 152 6256 42 H(245) 10143 292 5299 46 H(246) 8849 898 5033 41 H(252) 7359 490 5188 46 H(253) 6305 -158 5226 57 H(254) 4904 52 5757 60 H(255) 4560 858 6279 59 H(256) 5615 1493 6273 49 H(262) 6552 1855 4620 35 H(263) 6847 2489 3628 43 H(264) 8056 3050 3285 43 H(265) 8954 3014 3946 42 H(266) 8680 2371 4939 35 H(131) 9136 6779 8096 25 187 H(132) 10410 6333 8461 28 H(134) 9273 4704 9436 24 H(137) 8036 4303 9766 29 H(139) 5661 4409 9401 36 H(140) 5897 5398 8676 29 H(1S) 3429 8901 641 257 H(11A) 2788 9865 676 79 H(11B) 3724 9872 245 79 H(12A) 3612 10563 927 129 H(12B) 3419 9943 1494 129 H(12C) 4353 9949 1064 129 H(2S) 3637 10091 1049 243 H(21A) 4961 10349 540 123 H(21B) 4263 10610 106 123 H(22A) 5482 9983 -355 180 H(22B) 5341 9355 213 180 H(22C) 4645 9615 -220 180 H(3S) 3893 10049 180 127 H(31A) 4656 8913 702 97 H(31B) 3854 9013 373 97 H(32A) 3351 8840 1429 167 H(32B) 3771 9471 1420 167 H(32C) 2970 9570 1092 167 ________________________________________________________________________________ 188 Table 6. Torsion angles [°] for D19108. ________________________________________________________________ P(2)-N(7)-P(1)-C(51B) 77.2(4) P(2)-N(7)-P(1)-C(161) -49.65(18) P(2)-N(7)-P(1)-C(171) -168.39(14) P(2)-N(7)-P(1)-C(151) 73.0(2) N(7)-P(1)-C(151)-C(156) 21.4(4) C(161)-P(1)-C(151)-C(156) 148.2(4) C(171)-P(1)-C(151)-C(156) -95.8(4) N(7)-P(1)-C(151)-C(152) -160.7(4) C(161)-P(1)-C(151)-C(152) -33.9(4) C(171)-P(1)-C(151)-C(152) 82.2(4) C(156)-C(151)-C(152)-C(153) 0.8(7) P(1)-C(151)-C(152)-C(153) -177.2(4) C(151)-C(152)-C(153)-C(154) -1.5(9) C(152)-C(153)-C(154)-C(155) 4.8(11) C(153)-C(154)-C(155)-C(156) -7.3(10) C(152)-C(151)-C(156)-C(155) -3.4(7) P(1)-C(151)-C(156)-C(155) 174.6(4) C(154)-C(155)-C(156)-C(151) 6.7(8) N(7)-P(1)-C(51B)-C(56B) -12.9(9) C(161)-P(1)-C(51B)-C(56B) 117.8(8) C(171)-P(1)-C(51B)-C(56B) -129.4(8) N(7)-P(1)-C(51B)-C(52B) 166.0(7) 189 C(161)-P(1)-C(51B)-C(52B) -63.2(8) C(171)-P(1)-C(51B)-C(52B) 49.6(8) C(56B)-C(51B)-C(52B)-C(53B) -1.3(13) P(1)-C(51B)-C(52B)-C(53B) 179.8(8) C(51B)-C(52B)-C(53B)-C(54B) 4.3(16) C(52B)-C(53B)-C(54B)-C(55B) -11(2) C(53B)-C(54B)-C(55B)-C(56B) 13(2) C(52B)-C(51B)-C(56B)-C(55B) 4.4(15) P(1)-C(51B)-C(56B)-C(55B) -176.6(9) C(54B)-C(55B)-C(56B)-C(51B) -10.0(18) N(7)-P(1)-C(161)-C(166) -87.05(16) C(51B)-P(1)-C(161)-C(166) 140.8(4) C(171)-P(1)-C(161)-C(166) 31.21(17) C(151)-P(1)-C(161)-C(166) 148.2(2) N(7)-P(1)-C(161)-C(162) 88.43(16) C(51B)-P(1)-C(161)-C(162) -43.7(4) C(171)-P(1)-C(161)-C(162) -153.31(15) C(151)-P(1)-C(161)-C(162) -36.3(2) C(166)-C(161)-C(162)-C(163) -0.8(3) P(1)-C(161)-C(162)-C(163) -176.31(16) C(161)-C(162)-C(163)-C(164) 0.3(3) C(162)-C(163)-C(164)-C(165) 0.1(3) C(163)-C(164)-C(165)-C(166) -0.1(3) C(162)-C(161)-C(166)-C(165) 0.8(3) 190 P(1)-C(161)-C(166)-C(165) 176.28(16) C(164)-C(165)-C(166)-C(161) -0.4(3) N(7)-P(1)-C(171)-C(176) -9.90(17) C(51B)-P(1)-C(171)-C(176) 114.2(4) C(161)-P(1)-C(171)-C(176) -133.49(14) C(151)-P(1)-C(171)-C(176) 110.4(2) N(7)-P(1)-C(171)-C(172) 172.67(19) C(51B)-P(1)-C(171)-C(172) -63.3(4) C(161)-P(1)-C(171)-C(172) 49.1(2) C(151)-P(1)-C(171)-C(172) -67.0(3) C(176)-C(171)-C(172)-C(173) 0.2(4) P(1)-C(171)-C(172)-C(173) 177.7(2) C(171)-C(172)-C(173)-C(174) -0.7(5) C(172)-C(173)-C(174)-C(175) 0.3(5) C(173)-C(174)-C(175)-C(176) 0.5(4) C(174)-C(175)-C(176)-C(171) -0.9(3) C(172)-C(171)-C(176)-C(175) 0.5(3) P(1)-C(171)-C(176)-C(175) -176.92(14) P(1)-N(7)-P(2)-C(201) -0.57(18) P(1)-N(7)-P(2)-C(191) -122.77(15) P(1)-N(7)-P(2)-C(181) 120.07(15) N(7)-P(2)-C(181)-C(182) -11.82(14) C(201)-P(2)-C(181)-C(182) 113.97(13) C(191)-P(2)-C(181)-C(182) -130.09(13) 191 N(7)-P(2)-C(181)-C(186) 166.50(12) C(201)-P(2)-C(181)-C(186) -67.70(14) C(191)-P(2)-C(181)-C(186) 48.24(14) C(186)-C(181)-C(182)-C(183) -0.4(2) P(2)-C(181)-C(182)-C(183) 177.94(13) C(181)-C(182)-C(183)-C(184) -0.3(3) C(182)-C(183)-C(184)-C(185) 0.8(3) C(183)-C(184)-C(185)-C(186) -0.6(3) C(184)-C(185)-C(186)-C(181) -0.1(3) C(182)-C(181)-C(186)-C(185) 0.6(2) P(2)-C(181)-C(186)-C(185) -177.79(13) N(7)-P(2)-C(191)-C(196) 163.68(12) C(201)-P(2)-C(191)-C(196) 37.13(15) C(181)-P(2)-C(191)-C(196) -77.96(14) N(7)-P(2)-C(191)-C(192) -18.97(14) C(201)-P(2)-C(191)-C(192) -145.52(12) C(181)-P(2)-C(191)-C(192) 99.39(13) C(196)-C(191)-C(192)-C(193) -0.9(2) P(2)-C(191)-C(192)-C(193) -178.25(12) C(191)-C(192)-C(193)-C(194) 0.9(2) C(192)-C(193)-C(194)-C(195) -0.5(3) C(193)-C(194)-C(195)-C(196) 0.0(3) C(194)-C(195)-C(196)-C(191) 0.0(2) C(192)-C(191)-C(196)-C(195) 0.4(2) 192 P(2)-C(191)-C(196)-C(195) 177.73(12) N(7)-P(2)-C(201)-C(206) 90.10(15) C(191)-P(2)-C(201)-C(206) -147.20(13) C(181)-P(2)-C(201)-C(206) -31.81(15) N(7)-P(2)-C(201)-C(202) -85.95(15) C(191)-P(2)-C(201)-C(202) 36.75(16) C(181)-P(2)-C(201)-C(202) 152.14(14) C(206)-C(201)-C(202)-C(203) 0.7(3) P(2)-C(201)-C(202)-C(203) 176.76(15) C(201)-C(202)-C(203)-C(204) -1.0(3) C(202)-C(203)-C(204)-C(205) 0.2(3) C(203)-C(204)-C(205)-C(206) 0.9(3) C(204)-C(205)-C(206)-C(201) -1.2(3) C(202)-C(201)-C(206)-C(205) 0.4(3) P(2)-C(201)-C(206)-C(205) -175.69(14) P(4)-N(8)-P(3)-C(221) -52.2(2) P(4)-N(8)-P(3)-C(231) -170.62(16) P(4)-N(8)-P(3)-C(211) 71.22(19) N(8)-P(3)-C(211)-C(216) 115.23(15) C(221)-P(3)-C(211)-C(216) -118.30(15) C(231)-P(3)-C(211)-C(216) -2.33(17) N(8)-P(3)-C(211)-C(212) -64.02(18) C(221)-P(3)-C(211)-C(212) 62.45(18) C(231)-P(3)-C(211)-C(212) 178.43(17) 193 C(216)-C(211)-C(212)-C(213) 0.4(3) P(3)-C(211)-C(212)-C(213) 179.70(18) C(211)-C(212)-C(213)-C(214) 0.1(4) C(212)-C(213)-C(214)-C(215) -0.4(3) C(213)-C(214)-C(215)-C(216) 0.1(3) C(212)-C(211)-C(216)-C(215) -0.7(3) P(3)-C(211)-C(216)-C(215) -179.96(15) C(214)-C(215)-C(216)-C(211) 0.4(3) N(8)-P(3)-C(221)-C(222) 126.38(18) C(231)-P(3)-C(221)-C(222) -115.74(18) C(211)-P(3)-C(221)-C(222) 0.3(2) N(8)-P(3)-C(221)-C(226) -53.11(16) C(231)-P(3)-C(221)-C(226) 64.77(16) C(211)-P(3)-C(221)-C(226) -179.22(14) C(226)-C(221)-C(222)-C(223) 2.6(3) P(3)-C(221)-C(222)-C(223) -176.9(2) C(221)-C(222)-C(223)-C(224) -0.7(4) C(222)-C(223)-C(224)-C(225) -2.0(4) C(223)-C(224)-C(225)-C(226) 2.8(3) C(224)-C(225)-C(226)-C(221) -0.9(3) C(222)-C(221)-C(226)-C(225) -1.8(3) P(3)-C(221)-C(226)-C(225) 177.71(14) N(8)-P(3)-C(231)-C(232) 149.52(14) C(221)-P(3)-C(231)-C(232) 27.25(16) 194 C(211)-P(3)-C(231)-C(232) -88.90(15) N(8)-P(3)-C(231)-C(236) -32.73(16) C(221)-P(3)-C(231)-C(236) -155.00(14) C(211)-P(3)-C(231)-C(236) 88.85(15) C(236)-C(231)-C(232)-C(233) -0.2(3) P(3)-C(231)-C(232)-C(233) 177.50(14) C(231)-C(232)-C(233)-C(234) -0.8(3) C(232)-C(233)-C(234)-C(235) 1.1(3) C(233)-C(234)-C(235)-C(236) -0.5(3) C(232)-C(231)-C(236)-C(235) 0.9(3) P(3)-C(231)-C(236)-C(235) -176.90(15) C(234)-C(235)-C(236)-C(231) -0.5(3) P(3)-N(8)-P(4)-C(251) -99.35(18) P(3)-N(8)-P(4)-C(261) 21.5(2) P(3)-N(8)-P(4)-C(241) 140.66(17) N(8)-P(4)-C(241)-C(242) 18.58(18) C(251)-P(4)-C(241)-C(242) -101.23(17) C(261)-P(4)-C(241)-C(242) 143.58(16) N(8)-P(4)-C(241)-C(246) -160.45(16) C(251)-P(4)-C(241)-C(246) 79.74(18) C(261)-P(4)-C(241)-C(246) -35.45(18) C(246)-C(241)-C(242)-C(243) -0.8(3) P(4)-C(241)-C(242)-C(243) -179.84(17) C(241)-C(242)-C(243)-C(244) 0.4(3) 195 C(242)-C(243)-C(244)-C(245) 0.2(3) C(243)-C(244)-C(245)-C(246) -0.5(3) C(244)-C(245)-C(246)-C(241) 0.2(3) C(242)-C(241)-C(246)-C(245) 0.5(3) P(4)-C(241)-C(246)-C(245) 179.50(16) N(8)-P(4)-C(251)-C(252) -171.83(14) C(261)-P(4)-C(251)-C(252) 61.66(16) C(241)-P(4)-C(251)-C(252) -53.71(17) N(8)-P(4)-C(251)-C(256) 11.77(17) C(261)-P(4)-C(251)-C(256) -114.74(15) C(241)-P(4)-C(251)-C(256) 129.89(15) C(256)-C(251)-C(252)-C(253) 0.8(3) P(4)-C(251)-C(252)-C(253) -175.58(15) C(251)-C(252)-C(253)-C(254) 0.9(3) C(252)-C(253)-C(254)-C(255) -1.6(3) C(253)-C(254)-C(255)-C(256) 0.5(3) C(252)-C(251)-C(256)-C(255) -1.8(3) P(4)-C(251)-C(256)-C(255) 174.64(15) C(254)-C(255)-C(256)-C(251) 1.1(3) N(8)-P(4)-C(261)-C(262) -104.67(16) C(251)-P(4)-C(261)-C(262) 18.12(17) C(241)-P(4)-C(261)-C(262) 135.89(15) N(8)-P(4)-C(261)-C(266) 71.38(16) C(251)-P(4)-C(261)-C(266) -165.84(14) 196 C(241)-P(4)-C(261)-C(266) -48.07(16) C(266)-C(261)-C(262)-C(263) 0.5(3) P(4)-C(261)-C(262)-C(263) 176.54(15) C(261)-C(262)-C(263)-C(264) 0.1(3) C(262)-C(263)-C(264)-C(265) -1.2(3) C(263)-C(264)-C(265)-C(266) 1.6(3) C(264)-C(265)-C(266)-C(261) -1.0(3) C(262)-C(261)-C(266)-C(265) -0.1(3) P(4)-C(261)-C(266)-C(265) -176.21(15) N(1)-B(1)-C(11)-C(12) -42.59(18) C(31)-B(1)-C(11)-C(12) -155.72(14) C(21)-B(1)-C(11)-C(12) 74.51(17) N(1)-B(1)-C(11)-C(16) 140.78(15) C(31)-B(1)-C(11)-C(16) 27.7(2) C(21)-B(1)-C(11)-C(16) -102.11(17) C(16)-C(11)-C(12)-F(12) 175.29(13) B(1)-C(11)-C(12)-F(12) -1.7(2) C(16)-C(11)-C(12)-C(13) -3.3(2) B(1)-C(11)-C(12)-C(13) 179.67(15) F(12)-C(12)-C(13)-F(13) 6.2(2) C(11)-C(12)-C(13)-F(13) -175.16(15) F(12)-C(12)-C(13)-C(14) -174.32(15) C(11)-C(12)-C(13)-C(14) 4.4(3) F(13)-C(13)-C(14)-F(14) -0.9(2) 197 C(12)-C(13)-C(14)-F(14) 179.56(15) F(13)-C(13)-C(14)-C(15) 177.69(15) C(12)-C(13)-C(14)-C(15) -1.8(3) F(14)-C(14)-C(15)-F(15) -0.8(2) C(13)-C(14)-C(15)-F(15) -179.45(15) F(14)-C(14)-C(15)-C(16) 177.33(15) C(13)-C(14)-C(15)-C(16) -1.3(3) F(15)-C(15)-C(16)-F(16) -0.1(2) C(14)-C(15)-C(16)-F(16) -178.25(15) F(15)-C(15)-C(16)-C(11) -179.59(15) C(14)-C(15)-C(16)-C(11) 2.3(3) C(12)-C(11)-C(16)-F(16) -179.49(14) B(1)-C(11)-C(16)-F(16) -2.7(2) C(12)-C(11)-C(16)-C(15) 0.0(2) B(1)-C(11)-C(16)-C(15) 176.82(15) N(1)-B(1)-C(21)-C(26) -9.8(2) C(31)-B(1)-C(21)-C(26) 106.22(18) C(11)-B(1)-C(21)-C(26) -125.07(17) N(1)-B(1)-C(21)-C(22) 166.32(14) C(31)-B(1)-C(21)-C(22) -77.70(18) C(11)-B(1)-C(21)-C(22) 51.01(19) C(26)-C(21)-C(22)-F(22) -177.99(15) B(1)-C(21)-C(22)-F(22) 5.4(2) C(26)-C(21)-C(22)-C(23) 1.0(3) 198 B(1)-C(21)-C(22)-C(23) -175.60(16) F(22)-C(22)-C(23)-F(23) -1.2(3) C(21)-C(22)-C(23)-F(23) 179.76(17) F(22)-C(22)-C(23)-C(24) 178.75(16) C(21)-C(22)-C(23)-C(24) -0.3(3) F(23)-C(23)-C(24)-F(24) 0.6(3) C(22)-C(23)-C(24)-F(24) -179.40(17) F(23)-C(23)-C(24)-C(25) -179.85(17) C(22)-C(23)-C(24)-C(25) 0.2(3) F(24)-C(24)-C(25)-F(25) -1.5(3) C(23)-C(24)-C(25)-F(25) 178.96(17) F(24)-C(24)-C(25)-C(26) 178.68(17) C(23)-C(24)-C(25)-C(26) -0.9(3) C(22)-C(21)-C(26)-F(26) 178.13(15) B(1)-C(21)-C(26)-F(26) -5.6(3) C(22)-C(21)-C(26)-C(25) -1.7(2) B(1)-C(21)-C(26)-C(25) 174.55(16) F(25)-C(25)-C(26)-F(26) 2.1(2) C(24)-C(25)-C(26)-F(26) -178.10(16) F(25)-C(25)-C(26)-C(21) -178.06(16) C(24)-C(25)-C(26)-C(21) 1.8(3) N(1)-B(1)-C(31)-C(32) 115.46(16) C(11)-B(1)-C(31)-C(32) -129.18(16) C(21)-B(1)-C(31)-C(32) -4.1(2) 199 N(1)-B(1)-C(31)-C(36) -56.07(17) C(11)-B(1)-C(31)-C(36) 59.29(18) C(21)-B(1)-C(31)-C(36) -175.63(14) C(36)-C(31)-C(32)-F(32) -178.91(14) B(1)-C(31)-C(32)-F(32) 9.1(2) C(36)-C(31)-C(32)-C(33) 1.6(2) B(1)-C(31)-C(32)-C(33) -170.33(15) F(32)-C(32)-C(33)-F(33) -0.2(2) C(31)-C(32)-C(33)-F(33) 179.30(15) F(32)-C(32)-C(33)-C(34) -179.86(16) C(31)-C(32)-C(33)-C(34) -0.4(3) F(33)-C(33)-C(34)-F(34) 0.1(3) C(32)-C(33)-C(34)-F(34) 179.73(17) F(33)-C(33)-C(34)-C(35) 179.55(17) C(32)-C(33)-C(34)-C(35) -0.8(3) F(34)-C(34)-C(35)-F(35) -0.1(3) C(33)-C(34)-C(35)-F(35) -179.54(17) F(34)-C(34)-C(35)-C(36) -179.98(17) C(33)-C(34)-C(35)-C(36) 0.5(3) F(35)-C(35)-C(36)-F(36) -0.1(3) C(34)-C(35)-C(36)-F(36) 179.76(16) F(35)-C(35)-C(36)-C(31) -179.04(16) C(34)-C(35)-C(36)-C(31) 0.9(3) C(32)-C(31)-C(36)-F(36) 179.26(14) 200 B(1)-C(31)-C(36)-F(36) -8.2(2) C(32)-C(31)-C(36)-C(35) -1.9(2) B(1)-C(31)-C(36)-C(35) 170.61(16) N(2)-B(2)-C(41)-C(46) -133.88(14) C(51)-B(2)-C(41)-C(46) -15.3(2) C(61)-B(2)-C(41)-C(46) 111.07(16) N(2)-B(2)-C(41)-C(42) 45.40(18) C(51)-B(2)-C(41)-C(42) 164.01(13) C(61)-B(2)-C(41)-C(42) -69.65(18) C(46)-C(41)-C(42)-F(42) -177.38(13) B(2)-C(41)-C(42)-F(42) 3.3(2) C(46)-C(41)-C(42)-C(43) 1.2(2) B(2)-C(41)-C(42)-C(43) -178.14(14) F(42)-C(42)-C(43)-F(43) -2.5(2) C(41)-C(42)-C(43)-F(43) 178.89(14) F(42)-C(42)-C(43)-C(44) 177.70(14) C(41)-C(42)-C(43)-C(44) -0.9(2) F(43)-C(43)-C(44)-F(44) -0.1(2) C(42)-C(43)-C(44)-F(44) 179.71(14) F(43)-C(43)-C(44)-C(45) -179.98(14) C(42)-C(43)-C(44)-C(45) -0.2(2) F(44)-C(44)-C(45)-F(45) 1.4(2) C(43)-C(44)-C(45)-F(45) -178.73(14) F(44)-C(44)-C(45)-C(46) -179.02(14) 201 C(43)-C(44)-C(45)-C(46) 0.8(2) F(45)-C(45)-C(46)-F(46) 0.2(2) C(44)-C(45)-C(46)-F(46) -179.35(13) F(45)-C(45)-C(46)-C(41) 179.05(14) C(44)-C(45)-C(46)-C(41) -0.5(2) C(42)-C(41)-C(46)-F(46) 178.28(13) B(2)-C(41)-C(46)-F(46) -2.4(2) C(42)-C(41)-C(46)-C(45) -0.5(2) B(2)-C(41)-C(46)-C(45) 178.85(14) N(2)-B(2)-C(51)-C(52) 41.81(18) C(61)-B(2)-C(51)-C(52) 154.90(14) C(41)-B(2)-C(51)-C(52) -76.19(17) N(2)-B(2)-C(51)-C(56) -139.39(15) C(61)-B(2)-C(51)-C(56) -26.31(19) C(41)-B(2)-C(51)-C(56) 102.60(17) C(56)-C(51)-C(52)-F(52) -176.18(14) B(2)-C(51)-C(52)-F(52) 2.7(2) C(56)-C(51)-C(52)-C(53) 1.0(2) B(2)-C(51)-C(52)-C(53) 179.95(15) F(52)-C(52)-C(53)-F(53) -0.7(2) C(51)-C(52)-C(53)-F(53) -178.00(16) F(52)-C(52)-C(53)-C(54) 177.77(17) C(51)-C(52)-C(53)-C(54) 0.5(3) F(53)-C(53)-C(54)-F(54) -1.9(3) 202 C(52)-C(53)-C(54)-F(54) 179.60(17) F(53)-C(53)-C(54)-C(55) 177.58(18) C(52)-C(53)-C(54)-C(55) -0.9(3) F(54)-C(54)-C(55)-F(55) -1.2(3) C(53)-C(54)-C(55)-F(55) 179.26(18) F(54)-C(54)-C(55)-C(56) 179.26(18) C(53)-C(54)-C(55)-C(56) -0.3(3) F(55)-C(55)-C(56)-F(56) 2.8(3) C(54)-C(55)-C(56)-F(56) -177.65(17) F(55)-C(55)-C(56)-C(51) -177.57(17) C(54)-C(55)-C(56)-C(51) 2.0(3) C(52)-C(51)-C(56)-F(56) 177.33(15) B(2)-C(51)-C(56)-F(56) -1.6(2) C(52)-C(51)-C(56)-C(55) -2.2(2) B(2)-C(51)-C(56)-C(55) 178.87(16) N(2)-B(2)-C(61)-C(66) -127.62(15) C(51)-B(2)-C(61)-C(66) 116.89(16) C(41)-B(2)-C(61)-C(66) -11.0(2) N(2)-B(2)-C(61)-C(62) 55.53(17) C(51)-B(2)-C(61)-C(62) -59.96(17) C(41)-B(2)-C(61)-C(62) 172.15(13) C(66)-C(61)-C(62)-F(62) -178.62(14) B(2)-C(61)-C(62)-F(62) -1.4(2) C(66)-C(61)-C(62)-C(63) -0.2(2) 203 B(2)-C(61)-C(62)-C(63) 177.06(15) F(62)-C(62)-C(63)-F(63) -1.1(2) C(61)-C(62)-C(63)-F(63) -179.64(15) F(62)-C(62)-C(63)-C(64) 178.47(16) C(61)-C(62)-C(63)-C(64) 0.0(3) F(63)-C(63)-C(64)-F(64) -1.5(3) C(62)-C(63)-C(64)-F(64) 178.91(16) F(63)-C(63)-C(64)-C(65) 179.63(17) C(62)-C(63)-C(64)-C(65) 0.0(3) F(64)-C(64)-C(65)-F(65) 1.4(3) C(63)-C(64)-C(65)-F(65) -179.75(17) F(64)-C(64)-C(65)-C(66) -178.69(16) C(63)-C(64)-C(65)-C(66) 0.2(3) C(62)-C(61)-C(66)-F(66) 179.68(14) B(2)-C(61)-C(66)-F(66) 2.7(2) C(62)-C(61)-C(66)-C(65) 0.4(2) B(2)-C(61)-C(66)-C(65) -176.57(15) F(65)-C(65)-C(66)-F(66) 0.2(2) C(64)-C(65)-C(66)-F(66) -179.74(16) F(65)-C(65)-C(66)-C(61) 179.51(15) C(64)-C(65)-C(66)-C(61) -0.4(3) N(3)-B(3)-C(71)-C(76) 137.9(2) C(91)-B(3)-C(71)-C(76) 23.2(3) C(81)-B(3)-C(71)-C(76) -106.6(3) 204 N(3)-B(3)-C(71)-C(72) -48.8(2) C(91)-B(3)-C(71)-C(72) -163.45(19) C(81)-B(3)-C(71)-C(72) 66.8(2) C(76)-C(71)-C(72)-F(72) 178.4(3) B(3)-C(71)-C(72)-F(72) 4.2(3) C(76)-C(71)-C(72)-C(73) 2.7(4) B(3)-C(71)-C(72)-C(73) -171.5(3) F(72)-C(72)-C(73)-F(73) 2.8(4) C(71)-C(72)-C(73)-F(73) 178.7(2) F(72)-C(72)-C(73)-C(74) -176.3(3) C(71)-C(72)-C(73)-C(74) -0.5(4) F(73)-C(73)-C(74)-F(74) -2.0(4) C(72)-C(73)-C(74)-F(74) 177.1(3) F(73)-C(73)-C(74)-C(75) 178.2(3) C(72)-C(73)-C(74)-C(75) -2.7(4) F(74)-C(74)-C(75)-F(75) 1.9(4) C(73)-C(74)-C(75)-F(75) -178.3(3) F(74)-C(74)-C(75)-C(76) -176.5(3) C(73)-C(74)-C(75)-C(76) 3.3(4) C(72)-C(71)-C(76)-F(76) -178.3(3) B(3)-C(71)-C(76)-F(76) -4.5(4) C(72)-C(71)-C(76)-C(75) -2.0(4) B(3)-C(71)-C(76)-C(75) 171.7(3) F(75)-C(75)-C(76)-F(76) -2.9(4) 205 C(74)-C(75)-C(76)-F(76) 175.5(3) F(75)-C(75)-C(76)-C(71) -179.3(3) C(74)-C(75)-C(76)-C(71) -0.9(5) N(3)-B(3)-C(71A)-C(72A) -39.5(6) C(91)-B(3)-C(71A)-C(72A) -156.2(6) C(81)-B(3)-C(71A)-C(72A) 79.7(6) N(3)-B(3)-C(71A)-C(76A) 139.3(9) C(91)-B(3)-C(71A)-C(76A) 22.7(10) C(81)-B(3)-C(71A)-C(76A) -101.4(9) C(76A)-C(71A)-C(72A)-F(72A) -178.8(13) B(3)-C(71A)-C(72A)-F(72A) 0.1(13) C(76A)-C(71A)-C(72A)-C(73A) 3.8(14) B(3)-C(71A)-C(72A)-C(73A) -177.2(11) F(72A)-C(72A)-C(73A)-F(73A) 0(2) C(71A)-C(72A)-C(73A)-F(73A) 177.4(11) F(72A)-C(72A)-C(73A)-C(74A) -178.3(13) C(71A)-C(72A)-C(73A)-C(74A) -0.8(19) F(73A)-C(73A)-C(74A)-C(75A) 179.5(13) C(72A)-C(73A)-C(74A)-C(75A) -2(2) F(73A)-C(73A)-C(74A)-F(74A) 0(2) C(72A)-C(73A)-C(74A)-F(74A) 178.0(12) C(73A)-C(74A)-C(75A)-F(75A) -179.2(13) F(74A)-C(74A)-C(75A)-F(75A) 0.5(19) C(73A)-C(74A)-C(75A)-C(76A) 2(2) 206 F(74A)-C(74A)-C(75A)-C(76A) -178.1(12) C(72A)-C(71A)-C(76A)-F(76A) -176.7(11) B(3)-C(71A)-C(76A)-F(76A) 4.3(17) C(72A)-C(71A)-C(76A)-C(75A) -3.9(16) B(3)-C(71A)-C(76A)-C(75A) 177.1(10) C(74A)-C(75A)-C(76A)-F(76A) 174.2(13) F(75A)-C(75A)-C(76A)-F(76A) -4.5(19) C(74A)-C(75A)-C(76A)-C(71A) 1(2) F(75A)-C(75A)-C(76A)-C(71A) -177.5(11) N(3)-B(3)-C(81)-C(82) 138.19(14) C(91)-B(3)-C(81)-C(82) -106.13(16) C(71)-B(3)-C(81)-C(82) 24.1(2) C(71A)-B(3)-C(81)-C(82) 14.8(5) N(3)-B(3)-C(81)-C(86) -40.67(18) C(91)-B(3)-C(81)-C(86) 75.01(17) C(71)-B(3)-C(81)-C(86) -154.72(17) C(71A)-B(3)-C(81)-C(86) -164.1(5) C(86)-C(81)-C(82)-F(82) -176.81(13) B(3)-C(81)-C(82)-F(82) 4.2(2) C(86)-C(81)-C(82)-C(83) 2.6(2) B(3)-C(81)-C(82)-C(83) -176.37(14) F(82)-C(82)-C(83)-F(83) -0.3(2) C(81)-C(82)-C(83)-F(83) -179.78(14) F(82)-C(82)-C(83)-C(84) 178.67(14) 207 C(81)-C(82)-C(83)-C(84) -0.8(2) F(83)-C(83)-C(84)-F(84) -1.2(2) C(82)-C(83)-C(84)-F(84) 179.79(14) F(83)-C(83)-C(84)-C(85) 178.06(14) C(82)-C(83)-C(84)-C(85) -1.0(2) F(84)-C(84)-C(85)-F(85) 1.2(2) C(83)-C(84)-C(85)-F(85) -178.07(14) F(84)-C(84)-C(85)-C(86) 179.89(14) C(83)-C(84)-C(85)-C(86) 0.6(2) F(85)-C(85)-C(86)-F(86) 1.8(2) C(84)-C(85)-C(86)-F(86) -176.94(14) F(85)-C(85)-C(86)-C(81) -179.86(14) C(84)-C(85)-C(86)-C(81) 1.5(2) C(82)-C(81)-C(86)-F(86) 175.40(13) B(3)-C(81)-C(86)-F(86) -5.6(2) C(82)-C(81)-C(86)-C(85) -2.9(2) B(3)-C(81)-C(86)-C(85) 176.06(14) N(3)-B(3)-C(91)-C(92) 121.94(16) C(71)-B(3)-C(91)-C(92) -122.85(19) C(71A)-B(3)-C(91)-C(92) -115.4(3) C(81)-B(3)-C(91)-C(92) 4.4(2) N(3)-B(3)-C(91)-C(96) -54.84(17) C(71)-B(3)-C(91)-C(96) 60.4(2) C(71A)-B(3)-C(91)-C(96) 67.8(3) 208 C(81)-B(3)-C(91)-C(96) -172.36(13) C(96)-C(91)-C(92)-F(92) 179.80(15) B(3)-C(91)-C(92)-F(92) 2.9(3) C(96)-C(91)-C(92)-C(93) 0.3(2) B(3)-C(91)-C(92)-C(93) -176.61(16) F(92)-C(92)-C(93)-F(93) 0.6(3) C(91)-C(92)-C(93)-F(93) -179.87(16) F(92)-C(92)-C(93)-C(94) -178.80(16) C(91)-C(92)-C(93)-C(94) 0.7(3) F(93)-C(93)-C(94)-F(94) -1.1(3) C(92)-C(93)-C(94)-F(94) 178.30(15) F(93)-C(93)-C(94)-C(95) 178.94(16) C(92)-C(93)-C(94)-C(95) -1.6(3) F(94)-C(94)-C(95)-F(95) 2.6(2) C(93)-C(94)-C(95)-F(95) -177.45(15) F(94)-C(94)-C(95)-C(96) -178.42(14) C(93)-C(94)-C(95)-C(96) 1.5(2) F(95)-C(95)-C(96)-F(96) -0.1(2) C(94)-C(95)-C(96)-F(96) -179.07(14) F(95)-C(95)-C(96)-C(91) 178.48(14) C(94)-C(95)-C(96)-C(91) -0.5(2) C(92)-C(91)-C(96)-F(96) 178.12(14) B(3)-C(91)-C(96)-F(96) -4.7(2) C(92)-C(91)-C(96)-C(95) -0.4(2) 209 B(3)-C(91)-C(96)-C(95) 176.79(14) N(4)-B(4)-C(101)-C(102) 161.1(3) C(121)-B(4)-C(101)-C(102) -79.7(3) C(111)-B(4)-C(101)-C(102) 48.5(3) N(4)-B(4)-C(101)-C(106) -13.6(5) C(121)-B(4)-C(101)-C(106) 105.7(5) C(111)-B(4)-C(101)-C(106) -126.2(5) C(106)-C(101)-C(102)-F(102) -176.2(5) B(4)-C(101)-C(102)-F(102) 8.5(5) C(106)-C(101)-C(102)-C(103) 5.9(6) B(4)-C(101)-C(102)-C(103) -169.3(3) F(102)-C(102)-C(103)-F(103) 0.7(5) C(101)-C(102)-C(103)-F(103) 178.5(3) F(102)-C(102)-C(103)-C(104) 179.8(4) C(101)-C(102)-C(103)-C(104) -2.3(6) F(103)-C(103)-C(104)-F(104) -2.7(7) C(102)-C(103)-C(104)-F(104) 178.2(4) F(103)-C(103)-C(104)-C(105) 177.6(5) C(102)-C(103)-C(104)-C(105) -1.5(7) F(104)-C(104)-C(105)-F(105) 2.0(9) C(103)-C(104)-C(105)-F(105) -178.3(5) F(104)-C(104)-C(105)-C(106) -178.5(6) C(103)-C(104)-C(105)-C(106) 1.2(9) C(102)-C(101)-C(106)-F(106) 173.7(6) 210 B(4)-C(101)-C(106)-F(106) -11.3(9) C(102)-C(101)-C(106)-C(105) -6.3(9) B(4)-C(101)-C(106)-C(105) 168.7(6) F(105)-C(105)-C(106)-F(106) 2.5(10) C(104)-C(105)-C(106)-F(106) -176.9(6) F(105)-C(105)-C(106)-C(101) -177.5(6) C(104)-C(105)-C(106)-C(101) 3.0(11) N(4)-B(4)-C(01B)-C(06B) -33.9(10) C(121)-B(4)-C(01B)-C(06B) 82.9(11) C(111)-B(4)-C(01B)-C(06B) -143.7(10) N(4)-B(4)-C(01B)-C(02B) 146.1(4) C(121)-B(4)-C(01B)-C(02B) -97.0(5) C(111)-B(4)-C(01B)-C(02B) 36.3(5) C(06B)-C(01B)-C(02B)-F(02B) -173.6(10) B(4)-C(01B)-C(02B)-F(02B) 6.4(7) C(06B)-C(01B)-C(02B)-C(03B) 5.7(11) B(4)-C(01B)-C(02B)-C(03B) -174.3(6) F(02B)-C(02B)-C(03B)-F(03B) -0.9(10) C(01B)-C(02B)-C(03B)-F(03B) 179.7(6) F(02B)-C(02B)-C(03B)-C(04B) 179.1(7) C(01B)-C(02B)-C(03B)-C(04B) -0.3(10) F(03B)-C(03B)-C(04B)-F(04B) -1.4(12) C(02B)-C(03B)-C(04B)-F(04B) 178.6(7) F(03B)-C(03B)-C(04B)-C(05B) 174.8(10) 211 C(02B)-C(03B)-C(04B)-C(05B) -5.2(14) C(03B)-C(04B)-C(05B)-F(05B) -176.5(10) F(04B)-C(04B)-C(05B)-F(05B) -0.4(19) C(03B)-C(04B)-C(05B)-C(06B) 5(2) F(04B)-C(04B)-C(05B)-C(06B) -178.9(12) F(05B)-C(05B)-C(06B)-F(06B) 1(2) C(04B)-C(05B)-C(06B)-F(06B) 179.0(14) F(05B)-C(05B)-C(06B)-C(01B) -177.4(14) C(04B)-C(05B)-C(06B)-C(01B) 1(2) C(02B)-C(01B)-C(06B)-F(06B) 176.0(11) B(4)-C(01B)-C(06B)-F(06B) -4.0(19) C(02B)-C(01B)-C(06B)-C(05B) -6.2(19) B(4)-C(01B)-C(06B)-C(05B) 173.9(12) N(4)-B(4)-C(111)-C(116) 130.42(17) C(01B)-B(4)-C(111)-C(116) -121.0(3) C(121)-B(4)-C(111)-C(116) 15.6(2) C(101)-B(4)-C(111)-C(116) -113.1(2) N(4)-B(4)-C(111)-C(112) -53.04(19) C(01B)-B(4)-C(111)-C(112) 55.6(3) C(121)-B(4)-C(111)-C(112) -167.90(14) C(101)-B(4)-C(111)-C(112) 63.4(2) C(116)-C(111)-C(112)-F(112) 176.89(15) B(4)-C(111)-C(112)-F(112) -0.1(2) C(116)-C(111)-C(112)-C(113) -1.8(2) 212 B(4)-C(111)-C(112)-C(113) -178.77(15) F(112)-C(112)-C(113)-F(113) 1.5(2) C(111)-C(112)-C(113)-F(113) -179.77(15) F(112)-C(112)-C(113)-C(114) -177.77(15) C(111)-C(112)-C(113)-C(114) 1.0(3) F(113)-C(113)-C(114)-F(114) 0.4(3) C(112)-C(113)-C(114)-F(114) 179.61(16) F(113)-C(113)-C(114)-C(115) -178.72(16) C(112)-C(113)-C(114)-C(115) 0.5(3) F(114)-C(114)-C(115)-F(115) -0.6(3) C(113)-C(114)-C(115)-F(115) 178.47(16) F(114)-C(114)-C(115)-C(116) 179.89(16) C(113)-C(114)-C(115)-C(116) -1.0(3) C(112)-C(111)-C(116)-F(116) -177.98(15) B(4)-C(111)-C(116)-F(116) -1.3(3) C(112)-C(111)-C(116)-C(115) 1.3(3) B(4)-C(111)-C(116)-C(115) 178.00(16) F(115)-C(115)-C(116)-F(116) -0.1(3) C(114)-C(115)-C(116)-F(116) 179.36(16) F(115)-C(115)-C(116)-C(111) -179.42(16) C(114)-C(115)-C(116)-C(111) 0.1(3) N(4)-B(4)-C(121)-C(126) 126.36(17) C(01B)-B(4)-C(121)-C(126) 10.8(5) C(111)-B(4)-C(121)-C(126) -119.29(18) 213 C(101)-B(4)-C(121)-C(126) 4.5(3) N(4)-B(4)-C(121)-C(122) -51.12(19) C(01B)-B(4)-C(121)-C(122) -166.6(4) C(111)-B(4)-C(121)-C(122) 63.23(19) C(101)-B(4)-C(121)-C(122) -173.0(2) C(126)-C(121)-C(122)-F(122) 177.83(15) B(4)-C(121)-C(122)-F(122) -4.4(2) C(126)-C(121)-C(122)-C(123) -0.7(3) B(4)-C(121)-C(122)-C(123) 177.07(16) F(122)-C(122)-C(123)-F(123) 1.9(3) C(121)-C(122)-C(123)-F(123) -179.51(16) F(122)-C(122)-C(123)-C(124) -177.39(16) C(121)-C(122)-C(123)-C(124) 1.2(3) F(123)-C(123)-C(124)-F(124) -0.4(3) C(122)-C(123)-C(124)-F(124) 178.95(17) F(123)-C(123)-C(124)-C(125) 179.91(18) C(122)-C(123)-C(124)-C(125) -0.8(3) F(124)-C(124)-C(125)-F(125) 0.4(3) C(123)-C(124)-C(125)-F(125) -179.85(19) F(124)-C(124)-C(125)-C(126) -179.75(19) C(123)-C(124)-C(125)-C(126) 0.0(3) F(125)-C(125)-C(126)-F(126) 0.4(3) C(124)-C(125)-C(126)-F(126) -179.38(19) F(125)-C(125)-C(126)-C(121) -179.67(19) 214 C(124)-C(125)-C(126)-C(121) 0.5(3) C(122)-C(121)-C(126)-F(126) 179.74(17) B(4)-C(121)-C(126)-F(126) 2.1(3) C(122)-C(121)-C(126)-C(125) -0.2(3) B(4)-C(121)-C(126)-C(125) -177.78(18) C(135)-N(5)-C(131)-C(132) 3.1(2) Ru(1)-N(5)-C(131)-C(132) -170.14(12) N(5)-C(131)-C(132)-C(133) 0.3(3) C(131)-C(132)-C(133)-C(134) -2.9(2) C(131)-C(132)-C(133)-C(141) 174.53(15) C(134)-C(133)-C(141)-F(131) 112.4(11) C(132)-C(133)-C(141)-F(131) -65.0(11) C(134)-C(133)-C(141)-F(33B) -131.7(7) C(132)-C(133)-C(141)-F(33B) 50.9(7) C(134)-C(133)-C(141)-F(132) -13.7(5) C(132)-C(133)-C(141)-F(132) 168.9(5) C(134)-C(133)-C(141)-F(32B) -11.4(7) C(132)-C(133)-C(141)-F(32B) 171.2(7) C(134)-C(133)-C(141)-F(31B) 102.3(7) C(132)-C(133)-C(141)-F(31B) -75.1(7) C(134)-C(133)-C(141)-F(133) -133.6(5) C(132)-C(133)-C(141)-F(133) 49.0(6) C(132)-C(133)-C(134)-C(135) 2.0(2) C(141)-C(133)-C(134)-C(135) -175.33(15) 215 C(131)-N(5)-C(135)-C(134) -4.0(2) Ru(1)-N(5)-C(135)-C(134) 169.91(11) C(131)-N(5)-C(135)-C(136) 178.09(14) Ru(1)-N(5)-C(135)-C(136) -8.01(16) C(133)-C(134)-C(135)-N(5) 1.4(2) C(133)-C(134)-C(135)-C(136) 179.20(14) N(5)-C(135)-C(136)-N(6) 5.92(19) C(134)-C(135)-C(136)-N(6) -171.94(14) N(5)-C(135)-C(136)-C(137) -174.72(15) C(134)-C(135)-C(136)-C(137) 7.4(2) N(6)-C(136)-C(137)-C(138) 0.8(2) C(135)-C(136)-C(137)-C(138) -178.56(16) C(136)-C(137)-C(138)-C(139) -1.0(3) C(136)-C(137)-C(138)-C(142) 177.82(19) C(137)-C(138)-C(142)-F(34B) -103.2(9) C(139)-C(138)-C(142)-F(34B) 75.6(9) C(137)-C(138)-C(142)-F(135) 115.9(7) C(139)-C(138)-C(142)-F(135) -65.3(7) C(137)-C(138)-C(142)-F(36B) 25.1(11) C(139)-C(138)-C(142)-F(36B) -156.1(11) C(137)-C(138)-C(142)-F(35B) 135.0(9) C(139)-C(138)-C(142)-F(35B) -46.2(9) C(137)-C(138)-C(142)-F(136) -10.7(5) C(139)-C(138)-C(142)-F(136) 168.1(4) 216 C(137)-C(138)-C(142)-F(134) -125.2(5) C(139)-C(138)-C(142)-F(134) 53.6(5) C(137)-C(138)-C(139)-C(140) 0.3(3) C(142)-C(138)-C(139)-C(140) -178.52(19) C(138)-C(139)-C(140)-N(6) 0.7(3) C(139)-C(140)-N(6)-C(136) -0.9(2) C(139)-C(140)-N(6)-Ru(1) 179.59(14) C(137)-C(136)-N(6)-C(140) 0.2(2) C(135)-C(136)-N(6)-C(140) 179.55(14) C(137)-C(136)-N(6)-Ru(1) 179.73(12) C(135)-C(136)-N(6)-Ru(1) -0.90(17) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: 217 Table 7. Hydrogen bonds for D19108 [Å and °]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ C(196)-H(196)...F(44)#1 0.95 2.57 3.252(2) 129.2 C(222)-H(222)...F(55)#2 0.95 2.62 3.217(3) 121.0 C(131)-H(131)...F(86) 0.95 2.60 3.398(2) 142.3 C(132)-H(132)...F(45)#3 0.95 2.53 3.473(2) 170.5 C(140)-H(140)...F(52) 0.95 2.45 3.288(2) 147.0 O(1S^a)-H(1S^a)...F(125)#4 0.84 1.63 2.38(2) 148.0 C(11S^a)-H(11A^a)...F(115)#1 0.99 2.32 3.073(18) 132.3 C(12S^a)-H(12A^a)...F(116)#1 0.98 2.06 2.90(2) 143.3 C(12S^a)-H(12B^a)...F(93)#1 0.98 2.28 3.20(2) 157.4 C(21S^b)-H(21B^b)...F(116)#1 0.99 1.80 2.65(2) 141.8 C(22S^b)-H(22B^b)...F(116)#4 0.98 2.33 2.99(3) 123.9 O(3S^c)-H(3S^c)...F(116)#1 0.84 2.63 3.231(19) 129.3 C(31S^c)-H(31B^c)...F(124)#4 0.99 2.50 3.38(3) 147.0 C(31S^c)-H(31B^c)...F(125)#4 0.99 1.93 2.75(2) 138.3 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y+2,-z+1 #2 -x+1,-y+1,-z+1 #3 x+1,y,z #4 x,y,z-1 218  1 CHAPTER 1 INTRODUCTION: RENEWABLE ENERGY STORAGE Motivation: The Need for Storage Progress in generation of carbon-neutral renewable energy has been rapid over the last decade and is projected to grow to meet nearly half of world electricity demand by 2050 (Figure 1).1 As renewable energy becomes widespread and cost-competitive with fossil fuels, there will be increasing need for efficient, carbon-neutral storage technologies that can operate on a wide variety of time and power scales. 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% renewables natural gas Coal nuclear liquids 2010 2020 2030 2040 2050 Figure 1: Share of net electricity generation, world. Source: US. Energy Information Administration International Energy Outlook, September 2019 (Public Domain). 2 The most abundant sources of renewable energy, sunlight and wind, are intermittent and need to be stored at peak production to be used most efficiently. In California, where solar photovoltaics have become ubiquitous, the high production of solar energy has created a problem known as the “duck curve” (Figure 2).2 The peak of solar production occurs earlier in the day than peak electricity demand, resulting in a sharp rise in the net load on the grid as the sun sets, which requires generators to ramp up production very quickly. As solar gains even higher adoption rates, there will be an increasing number of sunny summer days where peak solar production outstrips demand and will need to be curtailed by grid operators, wasting energy. Wind power also varies on hourly, daily, and seasonal timescales that are uncoupled from demand, creating similar but even less predictable grid balancing and overgeneration problems.3 The grid-level ability to store energy from these intermittent sources during periods of high production to be used during periods of low production and high demand is key to reducing strain on power plants and electrical grids, lowering the cost of renewable energy, and increasing the penetration of renewables. Figure 2: Illustration of the “duck curve”. Created by Arnold Reinhold and reproduced under the Creative Commons Attribution-ShareAlike 4.0 International license. 3 A further challenge in the storage of renewable energy is applications such as long-range transportation and aviation which require energy sources that have a high energy density and fast refueling. These are the applications which are most difficult to transition from fossil fuels, which have high mass and volume energy densities (Figure 3).4 While there are increasing adoption rates for light duty electric vehicles, especially in large, newlyindustrialized countries such as China and India, the Li-ion batteries in those vehicles are too large and costly for heavy-duty applications such as freight transportation.5 Figure 3: Energy density comparison of transportation fuels. Source: Energy Information Administration (Public Domain). A wide variety of storage solutions will undoubtedly be needed for different sectors and different applications. Among the most efficient and flexible storage methods is electrochemical energy storage, wherein chemical oxidations and reductions store the energy – in short, batteries.6 The work in this dissertation represents fundamental science with potential applicability to two types of electrochemical energy storage technologies: hydrogen fuel cells and redox flow batteries. Hydrogen Evolution, Oxidation, and Fuel Cells Hydrogen derived from water splitting has been recognized as a key target for energy storage and fuel applications since the oil embargo of the 1970s.7,8 While the initial interest was in 4 developing alternatives to petroleum in order to secure energy independence from Middle Eastern oil producers, the climate crisis has renewed interest in hydrogen as a carbon-neutral energy source. Additionally, industrial feedstocks of hydrogen are currently primarily derived from steam reformation of hydrocarbons and the water-gas shift reaction, which are not only carbon intensive in their energy demands, but also produce CO2 as a coproduct.9 Development of renewable energy-fueled processes for producing hydrogen from water is therefore expected to be a key step toward the decarbonization of the global economy. Electro- or photoelectrocatalysts for the hydrogen evolution reaction (HER) are frequently targeted for use in the cathode of water electrolyzers, and there has been rapid progress in the development of Earth-abundant catalysts.10,11 However, a reversible catalyst which is also competent for the hydrogen oxidation reaction (HOR) has the advantage of being useful for water-based fuel cells, which are safer and more efficient than combustion at liberating energy from hydrogen. Hydrogen fuel cell cars additionally have several advantages over battery-powered electric vehicles, as they have longer driving ranges, faster refueling times, and are less disruptive to the electric grid.5 State-of-the-art commercial electolyzers and fuel cells both currently use Pt or IrO2 catalysts,12,13 which are too rare and expensive to be a scalable and economical solution long-term and are a major contributor to the higher cost of hydrogen cars.5 Thus, it is a critical area of research to identify Earth-abundant catalysts that are competent for HER and HOR to replace them. Naturally occurring hydrogenases are a typical source of inspiration in this field, since they are reversible and contain only Earth-abundant Fe and Ni.14 Indeed, a NiFe hydrogenase has been shown to catalyze HOR at a rate comparable to Pt.15 HOR catalyst development has occurred primarily in the solid-state material realm, but despite success in reducing the Pt loading for proton-exchange membrane (PEM) fuel cells,13 precious-metal-free catalysts are still unusual.16 Even less well-studied are Earth-abundant small-molecule catalysts which are capable of reversibly catalyzing the interconversion of protons and electrons with hydrogen. 5 Redox Flow Batteries Figure 4: Diagram of a vanadium-based redox flow battery. Reproduced with permission from the copyright holder, Elsevier, from reference 6. A redox flow battery (Figure 4) uses a solution-phase redox couple to store energy, as opposed to the solution-to-solid phase couples used by most conventional batteries. As the battery is charged, the charged electrolyte is pumped into a storage tank, and pumped back to the electrodes during discharge. Although it results in a low energy density, this design is advantageous for large, stationary applications such as grid balancing, since the capacity of the flow battery is as large as the storage tanks.6,17 Additionally, unlike hydrogen fuel cells, redox flow batteries have no need for catalysts to assist the charge and discharge process, as the transfer electrons directly with the electrode. A current limitation in redox flow battery technology is the reliance on water as the solvent. Water has an electrochemical stability window of only 1.23 V, limiting the cell voltage, and a high freezing point relative to outdoor temperatures during winter in much of the world. Non-aqueous redox flow battery electrolytes are desirable for applications where higher 6 voltages or lower working temperatures are needed, as there are many organic solvents which can overcome these limitations.18 In order to be a good candidate electrolyte for nonaqueous redox flow batteries, a molecule must have several properties. First, it must have a reversible electrochemical couple in the stability window of the desired solvent. Second, it must be stable in both the charged and discharged states over a long period of time and many charge/discharge cycles. Third, it should have high solubility in the solvent, which will improve the energy density of the battery. The difference in voltage between the reduction potentials of the two couples employed sets the maximum cell voltage. If the same molecule has two suitable couples, it can be used to make a symmetric redox flow battery, which confers additional stability to the system in the event of membrane crossover over time.19 Summary of this Dissertation Chapter Two of this dissertation focuses on one member of a series of macrocyclic Co catalysts that have been extensively studied for HER and its reaction with hydrogen. Further mechanistic information in this field is expected to aid the development of Earth-abundant catalysts for HER and HOR. Chapter Three of this dissertation describes the synthesis and boronation of a new Ru bipyridine cyanide complex. This work aimed to improve on previous work toward developing symmetric nonaqueous redox flow battery electrolytes using similar molecules. References (1) EIA projects that renewables will provide nearly half of world electricity by 2050 - Today in Energy - U.S. Energy Information Administration https://www.eia.gov/todayinenergy/detail.php?id=41533 (accessed Nov 6, 2019). (EIA) 7 (2) Confronting the Duck Curve: How to Address Over-Generation of Solar Energy https://www.energy.gov/eere/articles/confronting-duck-curve-how-address-overgeneration-solar-energy (accessed Nov 15, 2019). (3) Holttinen, H.; Meibom, P.; Orths, A.; Lange, B.; O’Malley, M.; Tande, J. O.; Estanqueiro, A.; Gomez, E.; Söder, L.; Strbac, G.; et al. Impacts of Large Amounts of Wind Power on Design and Operation of Power Systems, Results of IEA Collaboration. Wind Energy 2011, 14 (2), 179–192. https://doi.org/10.1002/we.410. (4) Few transportation fuels surpass the energy densities of gasoline and diesel - Today in Energy - U.S. Energy Information Administration (EIA) https://www.eia.gov/todayinenergy/detail.php?id=9991 (accessed Nov 15, 2019). (5) Cano, Z. P.; Banham, D.; Ye, S.; Hintennach, A.; Lu, J.; Fowler, M.; Chen, Z. Batteries and Fuel Cells for Emerging Electric Vehicle Markets. Nat. Energy 2018, 3 (4), 279–289. https://doi.org/10.1038/s41560-018-0108-1. (6) Alotto, P.; Guarnieri, M.; Moro, F. Redox Flow Batteries for the Storage of Renewable Energy: A Review. Renew. Sustain. Energy Rev. 2014, 29, 325–335. https://doi.org/10.1016/j.rser.2013.08.001. (7) Gray, H. B. Powering the Planet with Solar Fuel. Nat Chem 2009, 1 (1), 7–7. https://doi.org/10.1038/nchem.141. (8) Holladay, J. D.; Hu, J.; King, D. L.; Wang, Y. An Overview of Hydrogen Production Technologies. Catal. Today 2009, 139 (4), 244–260. https://doi.org/10.1016/j.cattod.2008.08.039. (9) Shaner, M. R.; Atwater, H. A.; Lewis, N. S.; McFarland, E. W. A Comparative Technoeconomic Analysis of Renewable Hydrogen Production Using Solar Energy. Energy Environ. Sci. 2016, 9 (7), 2354–2371. https://doi.org/10.1039/C5EE02573G. (10) Zou, X.; Zhang, Y. Noble Metal-Free Hydrogen Evolution Catalysts for Water Splitting. Chem. Soc. Rev. 2015, 44 (15), 5148–5180. https://doi.org/10.1039/C4CS00448E. 8 (11) McKone, J. R.; Marinescu, S. C.; Brunschwig, B. S.; Winkler, J. R.; Gray, H. B. EarthAbundant Hydrogen Evolution Electrocatalysts. Chem. Sci. 2014, 5 (3), 865–878. https://doi.org/10.1039/C3SC51711J. (12) Carmo, M.; Fritz, D. L.; Mergel, J.; Stolten, D. A Comprehensive Review on PEM Water Electrolysis. Int. J. Hydrog. Energy 2013, 38 (12), 4901–4934. https://doi.org/10.1016/j.ijhydene.2013.01.151. (13) Wang, Y.; Chen, K. S.; Mishler, J.; Cho, S. C.; Adroher, X. C. A Review of Polymer Electrolyte Membrane Fuel Cells: Technology, Applications, and Needs on Fundamental Research. Appl. Energy 2011, 88 (4), 981–1007. https://doi.org/10.1016/j.apenergy.2010.09.030. (14) Lubitz, W.; Ogata, H.; Rüdiger, O.; Reijerse, E. Hydrogenases. Chem. Rev. 2014, 114 (8), 4081–4148. https://doi.org/10.1021/cr4005814. (15) Jones, A. K.; Sillery, E.; Albracht, S. P. J.; Armstrong, F. A. Direct Comparison of the Electrocatalytic Oxidation of Hydrogen by an Enzyme and a Platinum Catalyst. Chem. Commun. 2002, No. 8, 866–867. https://doi.org/10.1039/B201337A. (16) Tian, X.; Zhao, P.; Sheng, W. Hydrogen Evolution and Oxidation: Mechanistic Studies and Material Advances. Adv. Mater. 2019, 31 (31), 1808066. https://doi.org/10.1002/adma.201808066. (17) Weber, A. Z.; Mench, M. M.; Meyers, J. P.; Ross, P. N.; Gostick, J. T.; Liu, Q. Redox Flow Batteries: A Review. J. Appl. Electrochem. 2011, 41 (10), 1137. https://doi.org/10.1007/s10800-011-0348-2. (18) Gong, K.; Fang, Q.; Gu, S.; Li, S. F. Y.; Yan, Y. Nonaqueous Redox-Flow Batteries: Organic Solvents, Supporting Electrolytes, and Redox Pairs. Energy Environ. Sci. 2015, 8 (12), 3515–3530. https://doi.org/10.1039/C5EE02341F. 9 (19) Potash, R. A.; McKone, J. R.; Conte, S.; Abruña, H. D. On the Benefits of a Symmetric Redox Flow Battery. J. Electrochem. https://doi.org/10.1149/2.0971602jes. Soc. 2016, 163 (3), A338–A344.  10 CHAPTER 2 KINETIC STUDIES OF HYDROGEN OXIDATION BY COBALOXIMES Introduction Cobaloximes as HER Catalysts Chart 1: Cobaloxime complexes. L is typically solvent or pyridine. In 1966, the first “cobaloximes” were synthesized by Schrauzer and Windgassen as models of the reduced form of vitamin B12, and they coined the term for this family of molecules by analogy to “cobalamin”.1 The reaction of dimethylglyoxime (usually abbreviated dmgH2) with cobaltous acetate resulted in the formation of a hydrogen-bonded macrocyclic complex, Co(dmgH)2L2, where the axial L sites are kinetically labile and usually occupied by solvent molecules. The remaining protons in the macrocycle can be replaced by BF2 on reaction with 11 BF3•Et2O,2 and the resulting complexes are generally much more stable, particularly in acid solution. Both reactions are quite general, and a number of similar complexes have been synthesized with varying substituents in the “backbone” of the diglyoxime macrocycle (Chart 1).3 Connolly and Espenson demonstrated in 1986 that trace amounts of Co(dmgBF2)2L2 catalyzed the evolution of H2 from acidic aqueous solutions of sufficiently reducing M(II) salts (M = Cr, Eu, V).4 They reported that the reaction slowed considerably in the absence of halide ions, leading them to conclude that the rate limiting step was inner-sphere electron transfer in a halide-bridged intermediate. Without rate-limiting H-H bond formation, the authors were unable to interrogate the mechanism of that step, and so they proposed two possible routes proceeding from a Co(III) hydride intermediate formed by the protonation of the reduced Co(I) form of the catalyst (Scheme 1, red and blue arrows). Scheme 1. Reproduced from reference 5 with permission from the copyright holder, American Chemical Society. This result was not further investigated until 2005, when both the Artero3 and Peters6 groups reported nonaqueous electrocatalytic proton reduction using cobaloxime catalysts. Artero and coworkers found that Co(dmgH)2(py)Cl electrocatalyzes HER from triethylammonium 12 chloride in DMF (pKa = 10.75) at the Co(II/I) couple (-0.98 V vs. Ag/AgCl). Notably, they report that substitution of BF2 for the bridging protons or H or Ph for the backbone methyls shifted the Co(II/I) couple anodically by ca. 100 mV, but shut down catalysis, suggesting that the Co(I) species formed were no longer basic enough to be protonated by triethylammonium. The authors considered the same general scheme as Connolly and Espenson, and concluded based on simulations of the cyclic voltammagrams that the heterolytic mechanism (Scheme 1, blue arrow) predominated under their catalytic conditions. In contrast, the Peters group found that the fluoroborated derivative Co(dmgBF2)2(MeCN)2 was a competent electrocatalyst for HER from trifluoroacetic acid (TFA) in MeCN (pKa = 12.7) at the Co(II/I) couple (-0.55 V vs. SCE). They also reported that the diphenylglyoxime congener Co(dpgBF2)2(MeCN)2 was a competent HER catalyst, but that the positive shift in the Co(II/I) couple relative to the methyl variant requires use of a stronger acid (HBF4•Et2O, pKa = 0.1) to maintain activity; neither complex showed activity when a weaker acid such as benzoic acid (pKa = 20.7) or TFA, respectively. Similar to Artero et al., Peters et al. used simulations of the catalytic cyclic voltammagrams to examine the mechanism of HER, but they concluded that the hemolytic mechanism (Scheme 1, red arrow) predominated for Co(dmgBF2)2(MeCN)2 and were unable to distinguish between the two mechanisms for Co(dpgBF2)2(MeCN)2. This pair of reports sparked a general interest in the use of cobaloximes for HER in a variety of contexts, including photocatalytic7–19 as well as electrocatalyic3,5,6,20 systems in both aqueous and organic solvents. Despite the ubiquity of these reports, however, a consensus mechanism never developed. There have been attempts to directly study the mechanism of cobaloxime-mediated HER, though the emerging picture has possibly become less clear rather than more. A 1971 report by Schrauzer and Holland21 identifying a “hydridocobaloxime” prepared by reduction with NaBH4 and stabilized by PBu3 trans to the hydride (Chart 2) has formed the basis for 13 mechanistic work from this apparent trapped intermediate. However, Artero et al. called into question the assignment of this complex as a classical metal hydride based on its purple color and the downfield 1H NMR resonance (~6 ppm) assigned as that of the hydride; a Co(III) hydride would be expected to be pale yellow with a hydride resonance upfield of 0 ppm.22 After repeating the experimental measurements and performing theoretical calculations, Artero reassigned the product as the ligand-protonated Co(I) tautomer of the original formulation with a hydride resonance of ~-5 ppm. Chart 2: Assignments of the structure of “hydridocobaloxime”. Top left, original assignment by Schrauzer and Holland;21 top right, reassignment by Artero et al.;22 bottom, major and minor products as assigned by Peters et al.23 More recently, the Peters group has again repeated that experimental characterization and found that the purple material which results from the NaBH4 reduction of Co(dmgH)2Cl(PBu3) does not correspond to a “hydridocobalxime” at all.23 Instead, the major product was confirmed by X-ray crystallography to be the Co-Co bonded dimer [Co(dmgH)2(PBu3)]2, with the apparent hydride signal arising from a paramagnetic trinuclear minor product. Alarmingly, this result invalidates mechanistic work which relied on this 14 incorrectly assigned “hydride”, including studies which measured the rate of H2 evolution from the material upon addition of acid24 as well as studies which assigned the spectra of various intermediates based on the spectrum of “hydridocobaloxime”.25 The most direct inspection of the mechanism of cobaloxime-mediated HER is a contribution from Dempsey and Gray in 2010 utilizing a strong photoacid and transient absorption spectroscopy to rapidly protonate [CoI(dmgBF2)2(MeCN)]-, allowing for the observation of the formation and decay of two intermediates prior to H2 evolution and generation of the Co(II).26 These intermediates were proposed to correspond first to the Co(III) hydride which results from protonation of the Co(I) anion, followed by the intermediate Co(II) hydride which results from reduction by excess Co(I). This final species is ultimately protonated again to release H2. This result demonstrated that further reduction of a Co(III) hydride is possible under catalytic conditions and may be necessary in order to render the metal hydride reactive enough to produce hydrogen. This pathway has more recently been proposed under electrocatalytic conditions based on foot-of-the-wave analysis and other electroanalytical chemistry methods.27,28 With this possibility under consideration, a second homolytic path (Scheme 1, violet arrow) may be added to the possibilities first proposed by Schrauzer. Also complicating the picture is the possibility for ligand noninnocence. The Peters group has investigated related macrocycles in which the oxime oxygens and bridging atoms on one half of the macrocycle have been replaced by hydrocarbon linkers (Chart 3), and these studies have highlighted the importance of ligand protonation in H-bridged cobaloxime systems.29 Aqueous HER catalysis by these complexes shows a Nernstian response consistent with a one-proton, one-electron process, while catalysis by Co(dmgBF2)2 complexes in MeCN does not, suggesting that protonation likely occurs on the ligand. 15 Chart 3: Cobalt diimine-dioxime complexes. Additionally, a report by the Norton group concerning high-pressure spectroscopy of Co(dmgBF2)2(MeCN)2 under 70 atm H2 features slow growth of optical and 1H NMR spectral features consistent with a solvent-assisted ligand-protonated product, suggesting that a ligand-protonated species could figure into catalysis even in the fluoroborated cobaloximes.30 Electrochemical analysis of Co(dmgBF2)2(MeCN)2 under high pressures of H2, however, cast doubt on this hypothesis, as the CoII/I couple is positioned ca. 300 mV more negative than at 1 atm, which suggests that ligand-protonated species would not be the observed catalyst even if it is generated.27 Figure 1: Proposed structure of the high-pressure reaction between H2 and Co(dmgBF2)2(MeCN)2 (L = MeCN). History of Cobaloximes as Hydrogenation and HOR Catalysts In the 1970s, the Simándi and Yamaguchi groups reported the first reactions of cobaloximes with dihydrogen, which resulted in decomposition via hydrogenation of the macrocyclic ligand.31–34 This decomposition can be outcompeted by catalytic hydrogenation if an 16 alternate substrate such as a Schiff base35 or styrene32 is present. Simándi et al. reported that the rate law for hydrogenation of styrene in MeOH and 1:1 MeOH:H2O is second-order in Co(dmgH)2 and first-order in H2, suggesting that the turnover-limiting step is homolytic activation of H2. They also reported that coordination of an axial pyridine in lieu of solvent (MeOH/H2O) enhanced the reaction rate by two orders of magnitude, highlighting the importance of understanding the effect of the axial ligands in cobaloxime systems. Complicating the matter, under most conditions the resting state of the cobaloxime is Co(II), a labile oxidation state that lends the molecule to readily undergo axial ligand substitution, leading to speciation if more than one viable ligand exists in solution.36 Similar axial ligand effects have surfaced in more recent years in both the HER12,37,38 and H2 activation39 literature. Simándi et al. also studied the reaction of Co(dmgH)2 complexes with H2 in the presence of strong Brønsted base and found it competent for HOR catalysis.31 As with styrene, the observed rate law is termolecular, but the HOR rate is enhanced relative to styrene hydrogenation, which implies that they cannot have the same intermediate in the rate-limiting step. Simándi et al. propose that deprotonation of one of the macrocyclic bridges produces a more active species for H2 activation, a suggestion which mirrors more recent observations of ligand protonation in HER. Norton et al. have more recently developed Co(dmgBF2)2 complexes under H2 as H-atom transfer catalysts for radical cyclizations.40 Kinetics experiments with a modified trityl radical and with TEMPO as H-atom acceptors resulted in a rate law second-order in Co, firstorder in H2, and independent of acceptor concentration or identity. This result suggests that substitution of BF2 at the bridging position does not change the turnover-limiting H2 activation found by Simándi et al. Further detailed mechanistic work from the Norton group has established that only the pentacoordinate Co(dmgBF2)2L is active, and that the identity of L can have a dramatic effect on the rate of reaction.39 Stronger donor ligands which labilize the trans ligand can case as much as an order of magnitude rate enhancement. By contrast, the rate is slowed by an order of magnitude by PPh3, which only singly ligates 17 Co(dmgBF2)2, which they attribute to enforcement of a pseudo-boat conformation in the macrocycle rather than the pseudo-chair observed in most crystal structures. The pseudoboat conformation may be sterically congested enough to slow bimolecular activation of H2. Studies of HOR in organic solvent with fluoroborated cobaloximes have been limited to a stoichiometric demonstration by the Peters group that with Co(dmgBF2)2(MeCN)2, but not Co(dpgBF2)2(MeCN)2, some degree of reversibility is possible using the conjugate bases of the acids used for HER catalysis.20 The reaction approaches an unfavorable (Keq = 0.03 atm1/2 ) equilibrium over the course of 34 with anisosbestic behavior, which the authors attribute to decomposition of the complex. Taken together, these reports display that the rate cobaloxime-mediated H2 activation in both HOR and hydrogenation reactions are markedly sensitive to changes in both the macrocycle and axial ligands. The third-order rate constants found by Simándi et al. range from ~103200 M-2s-1 for styrene hydrogenation by Co(dmgH)2, depending on the solvent and presence of added pyridine.32 When the reaction is instead HOR with strong base, they found a thirdorder rate constant of ~2200 M-2s-1.31 In MeCN, Norton et al. found a third-order rate constant of ~110 M-2s-1 for radical hydrogenation.40 This relatively slow oxidation of H2 in acetonitrile contrasts with the fast second-order rates (kapp = 7000 M-1s-1) observed for Co(dmgBF2)2(MeCN)2-catalyzed HER.6 Additional research is needed to clarify the mechanism of cobaloxime-mediated HER and HOR and the factors governing the reaction rates. 18 Results Scheme 2 The stoichiometric oxidation of hydrogen to protons by cobaloximes may proceed either via bimetallic homolytic H-H bond cleavage or deprotonation (heterolysis), and the balance of data in the literature suggests that both pathways are accessible (Scheme 2). Using the preequilibrium approximation for equations (1) and (3) and the steady-state approximation for [CoIII-H], a rate law emerges which is second-order in Co regardless of the dominant pathway (Equation 6). In this work, kinetic studies of Co(dmgBF2)2L2-mediated HOR were undertaken with the goal of determining whether this approximate rate law is appropriate and, if so, to measure the rate constants related to each pathway. By better understanding the bifurcation between these two pathways, insight may be gained into the microscopic-reverse HER. (6) [ ] = + [ ] [ ] [ ] [ ] 19 Selection of Base and Initial Kinetic Experiments Co(II) species are kinetically labile, and cobaloximes in this oxidation state rapidly exchange axial ligands. In order to simplify kinetic analysis and avoid solution speciation, a noncoordinating base was sought which would ensure that solvent was the only source of spectator axial ligands. The optical spectra of Co(dmgBF2)2(MeCN)2 solutions in MeCN were not altered by addition of N,N-dimethylaniline or 1,8-bis(dimethylamino)naphthalene (“proton sponge”), indicating neither displaces axial MeCN. Proton sponge is a relatively strong base (conjugate acid pKa in MeCN = 18.241), which favors the products side of the equilibrium, and an easy-to-handle solid at room temperature, making it an ideal candidate for initial studies. Addition of an atmosphere of H2 to a MeCN solution containing Co(dmgBF2)2(MeCN)2 and excess proton sponge resulted in the appearance of optical bands at 553 and 628 nm, consistent with the known spectrum of [Co(dmgBF2)2MeCN]- after an induction period of three hours (Figure 2).26 The [Co(dmgBF2)2MeCN]- spectrum continued to grow in isosbestically over the course of three days until all of the Co(dmgBF2)2(MeCN)2 had been converted to [Co(dmgBF2)2MeCN]-. The reaction did not reverse when the H2 atmosphere was removed and was not altered by the presence of the conjugate acid. 20 Figure 2: Time-dependent optical spectra of 1.9 mM Co(dmgBF2)2(MeCN)2 and 36 mM proton sponge in MeCN under 1 atm H2. Figure 3: Concentration of Co(I) over time based on absorption at 553 nm. 21 Varying the concentration of both the Co species and the base produced variable induction periods with no distinct pattern, but all reactions proceeded to completion over the course of 2-3 days. Plots of the natural logarithm, inverse, and inverse-square of concentration vs. time were all nonlinear even when the induction period was excluded from the data. Figure 4: Comparison of data from runs with different initial concentrations of Co(dmgBF2)2(MeCN)2 (Co) and proton sponger (PS). Initial Rate Experiments Using Proton Sponge The initial rate method is ideal for studying slow reactions, and was pursued along with higher concentration experiments to expedite data collection (Table 1, additional data in Supporting Data). The initial concentration of each reactant was systematically varied, and the average of a linear fit of the absorption data for the two Co(I) bands used to calculate the initial rate for each condition, truncating any observed induction period. The initial rate was not affected by variations in initial concentration of proton sponge. However, doubling the 22 initial pressure of H2 resulted in a doubling of the initial rate, and the initial rate varied with variations in the initial concentration of Co(dmgBF2)2(MeCN)2. A natural log-log plot of the initial rate vs. concentration was linear with a slope of 2.03 (Figure 5). Table 1: Initial rate data for the reaction of Co(dmgBF2)2(MeCN)2 (Co), proton sponge (B) and H2. Entry [Co]0 (mM) [B]0 (mM) P(H2) (atm) Initial Rate (M/s x 107) 1 5.8 8.5 1.0 3.4 2 6.0 4.3 1.0 3.3 3 6.0 2.1 1.0 3.2 4 4.6 2.2 1.0 1.9 5 3.0 2.1 1.0 0.91 6 1.7 2.2 1.0 0.23 7 5.8 25.2 1.0 4.4 8 6.2 19.7 0.50 1.9 9 6.3 19.7 0.25 0.86 23 Figure 5: Rate vs. concentration log-log plot for Co-varied runs and fit line. Slope = 2.03, R2 = 0.999. Extension to N,N-dimethylaniline Further initial rate experiments were pursued using N,N-dimethylaniline in order to understand the effect of base strength (conjugate acid pKa in MeCN = 11.442) on the kinetics of Co(dmgBF2)2(MeCN)2-mediated HOR. Induction periods prior to the appearance of [Co(dmgBF2)2MeCN]- bands were frequently observed. The concentration vs. time data became nonlinear within minutes, and the reaction did not proceed to completion after 24 h. After three days, the solution had reached equilibrium with an equilibrium constant of 1.3 x 10-5 atm-1/2. Removal of H2 resulted in a slow diminution of the [Co(dmgBF2)2MeCN]spectrum. 24 Figure 6: Example plots of absorbance over time for Co(dmgBF2)2(MeCN)2 and N,N-dimethylaniline under H2. Discussion Observed Induction Period The variable induction periods observed in these experiments likely occur due to trace O2 present in solution. Blue solutions of [Co(dmgBF2)2MeCN]- are rapidly converted to yellow Co(dmgBF2)2(MeCN)2 on exposure to air, and the induction periods observed were considerably longer when an ordinary Schlenk line (pressure ca. 50 mTorr) was used to degas induction period is then produced by rapid reoxidation of [Co(dmgBF2)2MeCN]- as it is produced at early time points. If this is the case, initial rate data recorded after the induction period ends should still be valid, since the reaction of interest is rate-limiting and therefore the induction period is simply obscuring the beginning of the linear data region. However, rigorous exclusion of oxygen or monitoring of the production of products not affected by trace oxygen (i.e. conjugate acid) would be desirable to verify this hypothesis and ensure the reliablility of the data collected. Additionally, for experiments with bases such as N,Ndimethylaniline which approach equilibrium rapidly relative to the length of the induction 25 period, enough of the linear data region may be obscured to render initial rates difficult to reliably extract. The source of the O2 is unclear, as solutions were prepared in a nitrogen-filled glovebox in Kontes valve-equipped cuvettes which were sufficiently gastight to prevent detectable leakage of H2 and degassed on a high-vacuum line before H2 addition from a line flushed with gas for several minutes. These conditions would ordinarily be considered rigorously free of O2; it is possible that this reaction is simply slow enough to observe the effects of unavoidable traces of O2 which remain despite the most rigorous efforts to eliminate it. Rate Law of HOR The initial rate data for Co(dmgBF2)2(MeCN)2-mediated HOR indicates a reaction that is second-order in Co, first-order in H2, and zero-order in proton sponge, with a rate constant of 3.8 ± .5 M-2s-1. This rate law suggests that only the homolytic pathway is accessed in this reaction, and the rate constant is smaller by two orders of magnitude than that measured by Norton with radical scavengers.40 The complete dominance of the homolytic pathway is unexpected, given that proton sponge is sufficiently basic to make the reaction irreversible, as evidenced by the final concentration of [Co(dmgBF2)2MeCN]- being equal to the initial concentration of Co(dmgBF2)2(MeCN)2, the observation that the reaction does not reverse when the H2 atmosphere is removed, and the lack of any effect on the reaction when the conjugate acid is present in solution. It is possible, then, that the pKa of the Co(III) hydride species is less than 18.2 in MeCN, but the pKa of the dihydrogen adduct is much higher. Recent work examining the relationship between acid identity and hydride formation rates in a related Co complex identified a departure from the linear free energy relationship with pKa when the acidic proton is sterically encumbered, as in N,N-dimethylanilinium.43 It is therefore also possible that the selection of a sterically encumbered base in order to preclude solution speciation has resulted 26 in a much slower deprotonation rate than would be expected based on pH, to the point where heterolysis cannot compete with homolysis. Further research would be needed to distinguish these effects. Alternate strategies for circumventing solution speciation, such as using a strong non-solvent axial ligand to push the speciation equilibrium far to one side or operating in a noncoordinating solvent such as CH2Cl2 would allow for unencumbered bases to be examined and analyzed unambiguously based on conjugate acid pKa. Conclusion Initial rate data suggests that the HOR mediated by Co(dmgBF2)2(MeCN)2 using proton sponge as the base proceeds by homolytic cleavage of the H-H bond. More experiments varying the base are needed to contextualize these results, as well as better methodology with respect to the exclusion of oxygen. References (1) Schrauzer, G. N.; Windgassen, R. J. Über Cobaloxime(II) Und Deren Beziehung Zum Vitamin B12r. Chem. Ber. 1966, 99 (2), 602–610. https://doi.org/10.1002/cber.19660990234. (2) Schrauzer, G. N.; Windgassen, R. J. Alkylcobaloximes and Their Relation to Alkylcobalamins. J. Am. Chem. Soc. 1966, 88 (16), 3738–3743. https://doi.org/10.1021/ja00968a012. (3) Razavet, M.; Artero, V.; Fontecave, M. Proton Electroreduction Catalyzed by Inorg. Chem. 2005, 44 (13), 4786– 4795. https://doi.org/10.1021/ic050167z. (4) Connolly, P.; Espenson, J. H. Cobalt-Catalyzed Evolution of Molecular Hydrogen. Inorg. 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Chem. 2011, 50 (8), 3404–3412. https://doi.org/10.1021/ic102317u. 28 (12) McCormick, T. M.; Han, Z.; Weinberg, D. J.; Brennessel, W. W.; Holland, P. L.; Eisenberg, R. Impact of Ligand Exchange in Hydrogen Production from CobaloximeContaining Photocatalytic Systems. Inorg. Chem. 2011, 50 (21), 10660–10666. https://doi.org/10.1021/ic2010166. (13) Dong, J.; Wang, M.; Zhang, P.; Yang, S.; Liu, J.; Li, X.; Sun, L. Promoting Effect of Electrostatic Interaction between a Cobalt Catalyst and a Xanthene Dye on Visible-LightDriven Electron Transfer and Hydrogen Production. J. Phys. Chem. C 2011, 115 (30), 15089–15096. https://doi.org/10.1021/jp2040778. (14) Zhang, P.; Wang, M.; Dong, J.; Li, X.; Wang, F.; Wu, L.; Sun, L. Photocatalytic Hydrogen Production from Water by Noble-Metal-Free Molecular Catalyst Systems Containing Rose Bengal and the Cobaloximes of BFx-Bridged Oxime Ligands. J. Phys. Chem. C 2010, 114 (37), 15868–15874. https://doi.org/10.1021/jp106512a. (15) Zhang, P.; Wang, M.; Li, C.; Li, X.; Dong, J.; Sun, L. Photochemical H2 Production with Noble-Metal-Free Molecular Devices Comprising a Porphyrin Photosensitizer and a Cobaloxime Catalyst. Chem. Commun. 2009, 46 (46), 8806–8808. https://doi.org/10.1039/C0CC03154B. (16) Probst, B.; Rodenberg, A.; Guttentag, M.; Hamm, P.; Alberto, R. A Highly Stable Limiting Steps. Inorg. Chem. 2010, 49 (14), 6453–6460. https://doi.org/10.1021/ic100036v. (17) Berben, L. A.; Peters, J. C. Hydrogen Evolution by Cobalt Tetraimine Catalysts Adsorbed on Electrode Surfaces. Chem. Commun. 2010, 46 (3), 398–400. https://doi.org/10.1039/B921559J. (18) Probst, B.; Kolano, C.; Hamm, P.; Alberto, R. An Efficient Homogeneous Intermolecular Rhenium-Based Photocatalytic System for the Production of H2. Inorg. Chem. 2009, 48 (5), 1836–1843. https://doi.org/10.1021/ic8013255. 29 (19) Du, P.; Schneider, J.; Luo, G.; Brennessel, W. W.; Eisenberg, R. Visible Light-Driven Hydrogen Production from Aqueous Protons Catalyzed by Molecular Cobaloxime Catalysts. Inorg. Chem. 2009, 48 (11), 4952–4962. https://doi.org/10.1021/ic900389z. (20) Hu, X.; Brunschwig, B. S.; Peters, J. C. Electrocatalytic Hydrogen Evolution at Low Overpotentials by Cobalt Macrocyclic Glyoxime and Tetraimine Complexes. J. Am. Chem. Soc. 2007, 129 (29), 8988–8998. https://doi.org/10.1021/ja067876b. (21) Schrauzer, G. N.; Holland, R. J. Hydridocobaloximes. J. Am. Chem. Soc. 1971, 93 (6), 1505–1506. https://doi.org/10.1021/ja00735a040. (22) Bhattacharjee, A.; Chavarot-Kerlidou, M.; Andreiadis, Eugen. S.; Fontecave, M.; Field, M. J.; Artero, V. Combined Experimental–Theoretical Characterization of the HydridoCobaloxime [HCo(DmgH)2(PnBu3)]. Inorg. Chem. 2012, 51 (13), 7087–7093. https://doi.org/10.1021/ic2024204. (23) Lacy, D. C.; Roberts, G. M.; Peters, J. C. The Cobalt Hydride That Never Was: Revisiting Schrauzer’s “Hydridocobaloxime.” J. Am. Chem. Soc. 2015, 137 (14), 4860– 4864. https://doi.org/10.1021/jacs.5b01838. (24) Chao, T.-H.; Espenson, J. H. Mechanism of Hydrogen Evolution from Hydridocobaloxime. J. Am. Chem. Soc. 1978, 100 (1), 129–133. https://doi.org/10.1021/ja00469a022. (25) and a Macrocyclic Cobalt Complex. Eur. J. Inorg. Chem. 2010, 2010 (17), 2488–2494. https://doi.org/10.1002/ejic.200901176. (26) Dempsey, J. L.; Winkler, J. R.; Gray, H. B. Mechanism of H2 Evolution from a Photogenerated Hydridocobaloxime. J. Am. Chem. Soc. 2010, 132 (47), 16774–16776. https://doi.org/10.1021/ja109351h. 30 (27) Wiedner, E. S.; Bullock, R. M. Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production. J. Am. Chem. Soc. 2016, 138 (26), 8309–8318. https://doi.org/10.1021/jacs.6b04779. (28) Rountree, E. S.; Martin, D. J.; McCarthy, B. D.; Dempsey, J. L. Linear Free Energy Relationships in the Hydrogen Evolution Reaction: Kinetic Analysis of a Cobaloxime Catalyst. ACS Catal. 2016, 6 (5), 3326–3335. https://doi.org/10.1021/acscatal.6b00667. (29) McCrory, C. C. L.; Uyeda, C.; Peters, J. C. Electrocatalytic Hydrogen Evolution in Acidic Water with Molecular Cobalt Tetraazamacrocycles. J. Am. Chem. Soc. 2012, 134 (6), 3164–3170. https://doi.org/10.1021/ja210661k. (30) Estes, D. P.; Grills, D. C.; Norton, J. R. The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics. J. Am. Chem. Soc. 2014, 136 (50), 17362–17365. https://doi.org/10.1021/ja508200g. (31) Simándi, L. I.; Budó-Záhonyi, É.; Szeverényi, Z. Effect of Strong Base on the Activation of Molecular Hydrogen by Pyridinebis(Dimethylglyoximato)Cobalt(II). Inorg. Nucl. Chem. Lett. 1976, 12 (3), 237–241. https://doi.org/10.1016/0020-1650(76)80158-4. (32) Simándi, L. I.; Szeverényi, Z.; Budó-Záhonyi, É. Activation of Molecular Hydrogen by Cobaloxime(II) Derivatives. Inorg. Nucl. Chem. Lett. 1975, 11 (11), 773–777. https://doi.org/10.1016/0020-1650(75)80098-5. (33) Yamaguchi, T.; Miyagawa, R. The Effect of Pyridine on the Hydrogen Absorption Process of Bis(Dimethylglyoximato)Cobalt(Ii). Chem. Lett. 1978, 7 (1), 89–92. https://doi.org/10.1246/cl.1978.89. (34) Yamaguchi, T.; Tsumura, T. The Effect of Triphenylphosphine on the Hydrogenation Reaction of Bis(Dimethylglyoximato)Cobalt(Ii). Chem. Lett. 1973, 2 (4), 409–412. https://doi.org/10.1246/cl.1973.409. 31 (35) Yamaguchi, T.; Nakayama, M.; Tsumura, T. The Effect of Base Strength of Schiff Bases on Their Catalytic Hydrogenation with Bis(Dimethylglyoximato)Cobalt(Ii). Chem. Lett. 1972, 1 (12), 1231–1234. https://doi.org/10.1246/cl.1972.1231. (36) Lawrence, M. A. W.; Celestine, M. J.; Artis, E. T.; Joseph, L. S.; Esquivel, D. L.; Ledbetter, A. J.; Cropek, D. M.; Jarrett, W. L.; Bayse, C. A.; Brewer, M. I.; et al. Computational, Electrochemical, and Spectroscopic Studies of Two Mononuclear Cobaloximes: The Influence of an Axial Pyridine and Solvent on the Redox Behaviour and Evidence for Pyridine Coordination to Cobalt(I) and Cobalt(II) Metal Centres. Dalton Trans. 2016, 45 (25), 10326–10342. https://doi.org/10.1039/C6DT01583B. (37) Basu, D.; Mazumder, S.; Niklas, J.; Baydoun, H.; Wanniarachchi, D.; Shi, X.; Staples, R. J.; Poluektov, O.; Schlegel, H. B.; Verani, C. N. Evaluation of the Coordination Preferences and Catalytic Pathways of Heteroaxial Cobalt Oximes towards Hydrogen Generation. Chem. Sci. 2016, 7 (5), 3264–3278. https://doi.org/10.1039/C5SC04214C. (38) Panagiotopoulos, A.; Ladomenou, K.; Sun, D.; Artero, V.; Coutsolelos, A. G. Photochemical Hydrogen Production and Cobaloximes: The Influence of the Cobalt Axial N-Ligand on the System Stability. Dalton Trans. 2016, 45 (15), 6732–6738. https://doi.org/10.1039/C5DT04502A. (39) Li, G.; Estes, D. P.; Norton, J. R.; Ruccolo, S.; Sattler, A.; Sattler, W. Dihydrogen Activation by Cobaloximes with Various Axial Ligands. Inorg. Chem. 2014, 53 (19), 10743– 10747. https://doi.org/10.1021/ic501975r. (40) Li, G.; Han, A.; Pulling, M. E.; Estes, D. P.; Norton, J. R. Evidence for Formation of a Co–H Bond from (H2O)2Co(DmgBF2)2 under H2: Application to Radical Cyclizations. J. Am. Chem. Soc. 2012, 134 (36), 14662–14665. https://doi.org/10.1021/ja306037w. (41) Ozeryanskii, V. A.; Pozharskii, A. F.; Milgizina, G. R.; Howard, S. T. Synthesis and Properties of 5,6Easily-Modified Basicity. J. https://doi.org/10.1021/jo001171p. Org. Chem. 2000, 65 (22), 7707–7709. 32 (42) Tshepelevitsh, S.; Kütt, A.; Lõkov, M.; Kaljurand, I.; Saame, J.; Heering, A.; Plieger, P. G.; Vianello, R.; Leito, I. On the Basicity of Organic Bases in Different Media. Eur. J. Org. Chem. 2019, 2019 (40), 6735–6748. https://doi.org/10.1002/ejoc.201900956. (43) Elgrishi, N.; Kurtz, D. A.; Dempsey, J. L. Reaction Parameters Influencing Cobalt Hydride Formation Kinetics: Implications for Benchmarking H2-Evolution Catalysts. J. Am. Chem. Soc. 2017, 139 (1), 239–244. https://doi.org/10.1021/jacs.6b10148. (44) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Safe and Convenient Procedure for Solvent Purification. Organometallics 1996, 15 (5), 1518– 1520. https://doi.org/10.1021/om9503712. 33 Methods General Considerations Unless stated otherwise, all manipulations were carried out in a nitrogen-filled glovebox or under nitrogen or argon using standard Schlenk techniques. Dry, air-free solvents were obtained from a Grubbs-type solvent purification system.44 Co(dmgBF2)2(MeCN)2 was synthesized by a literature method26 and its purity confirmed by cyclic voltammetry prior to use. Proton sponge and N,N-dimethylaniline were ordered from Sigma-Aldrich and used as received. UV-Vis spectra were recorded on a Cary Bio 50 spectrometer. General Procedure for Kinetics Experiments A solution of Co(dmgBF2)2(MeCN)2 and base (proton sponge or N,N-dimethylaniline) was prepared in MeCN. A 1 mm path length, Kontes valve-sealed cuvette equipped with a sidearm bulb and a stirbar was charged with the solution and degassed on a high-vacuum line by the freeze-pump-thaw method twice. The solution was allowed to warm to room temperature before H2 was added to the desired pressure. The reaction was monitored by UV-Vis spectroscopy by tipping the solution into the cuvette at the desired intervals and was stirred in the side-arm bulb between spectra. 34 Supporting Data Figure S1: Initial rate plot for Table 1 entry 1, calculated based on absorbance at 553 nm. Figure S2: Initial rate plot for Table 1 entry 1, calculated based on absorbance at 628 nm. 35 Figure S3: Initial rate plot for Table 1 entry 2, calculated based on absorbance at 553 nm. Figure S4: Initial rate plot for Table 1 entry 2, calculated based on absorbance at 628 nm. 36 Figure S5: Initial rate plot for Table 1 entry 3, calculated based on absorbance at 553 nm. Figure S6: Initial rate plot for Table 1 entry 3, calculated based on absorbance at 628 nm. 37 Figure S7: Initial rate plot for Table 1 entry 4, calculated based on absorbance at 553 nm. Figure S8: Initial rate plot for Table 1 entry 4, calculated based on absorbance at 628 nm. 38 Figure S9: Initial rate plot for Table 1 entry 5, calculated based on absorbance at 553 nm. Figure S10: Initial rate plot for Table 1 entry 5, calculated based on absorbance at 628 nm. 39 Figure S11: Initial rate plot for Table 1 entry 6, calculated based on absorbance at 553 nm. Figure S12: Initial rate plot for Table 1 entry 6, calculated based on absorbance at 628 nm. 40 Figure S13: Initial rate plot for Table 1 entry 7, calculated based on absorbance at 553 nm. Figure S14: Initial rate plot for Table 1 entry 7, calculated based on absorbance at 628 nm. 41 Figure S15: Initial rate plot for Table 1 entry 8, calculated based on absorbance at 553 nm. Figure S16: Initial rate plot for Table 1 entry 8, calculated based on absorbance at 628 nm. 42 Figure S17: Initial rate plot for Table 1 entry 9, calculated based on absorbance at 553 nm Figure S18: Initial rate plot for Table 1 entry 9, calculated based on absorbance at 628 nm.  43 CHAPTER 3 SYNTHESIS, SPECTROSCOPY AND BORONATION OF A NEW HETEROLEPTIC RUTHENIUM CYANIDE COMPLEX Introduction [Ru(diimine)(CN)4] 2- complexes Figure 1: Structure of [Ru(bpy)(CN)4]2-. Inspired by mounting evidence that the long-lived metal-to-ligand charge transfer (MLCT) excited state of [Ru(bpy)3]2+ featured an electron localized on just one bpy ligand, Scandola et al. first synthesized [Ru(bpy)(CN)4]2- (Figure 1) in 1986 as a minimalistic model of Ru(II) diimine photosensitizers.1 They observed that the luminescence and excited-state properties were very similar to [Ru(bpy)3]2+, but that the spectroscopic properties also featured strong solvatochromism. The magnitude of 44 the solvatochromism is driven largely by specific solvent interactions with the cyanide ligands. In a systematic study of Ru-polypyridyl-cyanide complexes with 15 cyanides, Meyer et al. found that shifts in the C-N stretching frequency, MLCT absorption energy, and emission energy all correlated with the Gutmann acceptor number of the solvent and increased as a function of the number of cyanide ligands.2 These solvatochromic properties have driven much of the interest in [Ru(bpy)(CN)4]2- and related [Ru(diimine)(CN)4]2- complexes,3–5 and several applications have been reported. PPN2 Ru(bpy)(CN)4 (PPN = bis(triphenylphosphine)iminium) can be used as a humidity sensor, as it reversibly turns from purple to yellow on exposure to water vapor.6 Solvent-tunable dye sensitized solar cells have been produced using a carboxylate-modified bpy to append the molecule to TiO2.7 The exposed lone pair on the cyanide nitrogen in [Ru(diimine)(CN)4]2- complexes has also been exploited to form supramolecular assemblies through hydrogen bonding8–13 or coordination to other metal centers.14–21 These assemblies often have interesting luminescence or energy-transfer properties, and one such assembly has been exploited as a sensor and chemodosimeter for amines released during food spoilage.15,16 Borane Modification of Metal Cyanide Complexes In 1963, Shriver observed that a number of cyanometallates could absorb an equivalent of borane per cyanide, resulting in a ca. 100 cm-1 shift in the C-N stretch to higher frequencies.22 For the homoleptic cyanometallates, he found that the d-d transitions were unaffected by the coordination of borane, but the spectrum of Fe(phen)2(CN)2, which is dominated by MLCT transitions, blueshifted dramatically. This pair of observations indicates that formation of the borane adduct stabilizes metal-centered orbitals, but has no strong effect on the ligand-based orbitals. As a 45 result, one expects that d-d transitions should remain relatively constant, MLCT transitions should blueshift, and ligand-to-metal charge transfer (LMCT) transitions should redshift on boronation; electrochemically, the same orbital shifts should produce anodic shifts in metal-centered redox processes while minimally affecting ligand-centered redox processes. While this area of research had been fairly dormant since Shriver’s work, it became of interest to the Gray group as a way of tuning the potential of cyanometallates in order to produce high-voltage redox flow battery electrolytes. As expected, McNicholas et al. found that addition of boranes to ferricyanide anodically shift the FeII/III couple.23 By examining cyclic voltammagrams containing substoichiometric BPh3, which coordinates reversibly to the cyanides, they determined that there is a linear relationship between the number of boranes coordinated and the magnitude of the shift. Each equivalent of BPh3 shifts the ferricyanide couple by ca. 260 mV, and for BCF, which coordinates irreversibly, a more dramatic 350 mV shift was observed. These observations were in line with previous publications which showed similar shifts in OsII/III 24 and ReI/II couples25 on addition of the same boranes to cyanide ligands. As of this writing, the study of boronation of homoleptic cyanometallates is very active within the Gray group, and manuscripts are now in preparation describing synthesis and spectroscopy of Co, Mn, Cr, Fe, Ru, Os, Ni, and Pt isocyanoborate complexes.26–28 Previous Work on Boronation of [Ru(bpy)(CN)4] 2- and related complexes In an effort to develop symmetric redox flow battery electrolytes, the boronation of Fe(II) and Ru(II) cyanometallates containing bpy and phen has also been studied recently in the Gray group.26,29 [Ru(bpy)(CN)4]2-, [Fe(bpy)(CN)4]2-, and [Fe(phen)(CN)4]2- were each boronated with both BPh3 and BCF. In each case, 46 boronation produces a shift to higher frequency of the C-N stretches, a blueshift in the MLCT-dominated optical spectrum, and an anodic shift of the MII/III couple, with more dramatic shifts for BCF than BPh3, reflecting its higher Lewis acidity. In the case of [Ru(bpy)(CN)4]2--, boronation also results in a luminescent excited state that is two orders of magnitude longer-lived, although the BPh3 adduct undergoes photodecomposition with loss of the borane. Although a redox flow battery has not yet been successfully created from it, this research resulted in the synthesis of [Ru(bpy)(CN-BCF)4]2--, which in MeCN has two reversible redox events separated by more than 3.5 V. This voltage would greatly improve upon the working voltages of existing flow battery systems. The following work represents an effort to improve the reductive stability of this molecule. Results & Discussion Synthesis and Spectroscopy of [Ru(CF3bpy)(CN)4] 2K2Ru(CF3bpy)(CN)4 (CF3bpy = 4,4’-bis(trifluoromethyl)-2,2’-bipyridine) was synthesized analogously to other K2Ru(diimine)(CN)4 complexes30 and converted to the PPN salt by precipitation from aqueous solution. PPN2Ru(CF3bpy)(CN)4 is received initially as a brick-red solid which is soluble in polar organic solvents and turns dark green when fully dehydrated. The complex was characterized by 1H and 19 F NMR spectroscopy, solid-state IR spectroscopy, elemental analysis, and X-ray crystallography. 47 Figure 2: Molecular structure of PPN2Ru(CF3bpy)(CN)4. Thermal ellipsoids set at 50% probability. Cations, hydrogen atoms, and solvent molecules omitted for clarity. The X-ray crystallographic data (Figure 2) reveals a negligible difference in metalligand contacts between [Ru(CF3bpy)(CN)4]2- and the parent bpy complex,6 which suggests that there is minimal difference in backbonding, despite the more electrondeficient bipyridine ligand. The C-N stretches detected in the solid state by FT-IR spectroscopy (Figure 3) support this interpretation. Typical complexes in this family have three closely-spaced strong peaks between 2030-2060 cm-1 and a weaker peak around 2090 cm-1; the closely-spaced peaks were not resolved, but the observed peaks at 2062 and 2090 cm-1 are in line with related complexes. 48 Figure 3: IR spectrum of PPN2Ru(CF3bpy)(CN)4 with CN stretches highlighted in inset. 49 Figure 4: UV-Vis spectra of [Ru(CF3bpy)(CN)4]2- in water (red broken trace, K salt) and acetonitrile (green solid trace, PPN salt). [Ru(diimine)(CN)4]2- complexes are well-known for their solvatochromism, which results both from having a ground-state dipole which interacts with polar solvents and the ability to accept hydrogen bonds at the N-termini of the cyanide ligands.5 Likewise, [Ru(CF3bpy)(CN)4]2- displays strong solvatochromism, with the lowestenergy MLCT transition redshifting ca. 5500 cm-1 when the solvent is changed from water to acetonitrile (Figure 4). In water, the spectrum displays three distinct bands, which can be assigned as two MLCT transitions and a CF3bpy- - based on their extinction coefficients (~103 M-1cm-1 for MLCT transitions and ~104 - -1 ), indicating that cyanide lone pair interactions are able to shift the d(Ru) orbitals while minimally affecting the 50 CF3 bpy orbitals. The absorption bands are also redshifted relative to most other [Ru(diimine)(CN)4]2- complexes (Table 1), reflecting the low-l CF3 bpy relative to bpy and other commonly-used diimines. In this respect, CF3bpy displays similar electronic properties to bpz, but without the exposed lone pairs which hydrogen bond with water. Table 1: Comparison of room temperature photophysical data for [Ru(CF3bpy)(CN)4]2and selected [Ru(diimine)(CN)4]2- complexes. Rbpy indicates R in the 4,4’ positions of bipyridine. Diimine ligand Solvent max (nm)( bpy H2O 400 610(101) 1 H2O 404(4100) 624(100) 11 MeCN 535 790(7) 8 H2O 392 600(115) 31 MeCN 530 780(7) 31 D2O 437(2200) (3.4) 19 MeCN 575 (0.25) 19 H2O 465(5700) 704(5) 32 MeCN 554 HOOC MeCN 515 750 7 CF3 H2O 443(3170) 706 This work MeCN 589(3770) N.O. below 930 This work Me bpy bpym bpz bpy bpy (M-1 cm-1)) em (nm) ( (ns)) Reference 32 While [Ru(diimine)(CN)4]2- displays weak luminescence in aqueous solution (Figure S6), no luminescence was observed in the solid state or 2-MeTHF solution at room temperature or 77 K, suggesting that the emission in the dehydrated form may be redshifted beyond the 930 nm detection limit of the instruments used. 51 Figure 5: Cyclic voltammagram of 33 mM PPN2 Ru(CF3bpy)(CN)4 in 0.2 M Bu4NPF6-supported acetonitrile. Working electrode: glassy carbon. Counter electrode: Pt wire. The cyclic voltammagram of PPN2 Ru(CF3bpy)(CN)4 in 0.2 M Bu4NPF6-supported acetonitrile displays two redox events at 0.05 and -1.92 V vs. Fc+/0 corresponding to oxidation of the metal center to Ru(III) and reduction of the CF3 bpy ligand, respectively (Figure 5). The peak current ratios for both waves are close to unity and the peak-to-peak separations are ca. 79 mV and independent of scan rate, indicating diffusion-controlled reversible electron transfer. While the parent bpy complex features a second irreversible reduction presumed to be deligation of bpy2-,33 no such reduction or decomposition is observed for [Ru(CF3bpy)(CN)4]2-. The reductive stability of CF3bpy in this system is accompanied by a 330 mV anodic shift in the bpy0/- couple relative to the parent complex and a 230 mV anodic shift in the Ru2+/3+ 52 couple. These shifts indicate that not only is CF3bpy more easily reduced than bpy, but that inductive effects result in a harder to oxidize Ru center. Boronation with BCF and Spectroscopy The tris(pentafluorophenyl)borane (BCF) adduct PPN2 Ru(CF3bpy)(CN-BCF)4 was prepared in inert atmosphere by mixing DCM solutions of PPN2 Ru(CF3bpy)(CN)4 and BCF and heating. On addition of the colorless BCF solution, the dark green PPN2 Ru(CF3bpy)(CN)4 solution rapidly turns yellow. The resulting complex is an airstable, luminescent yellow solid which is extremely soluble in polar organic solvents and has been characterized by 1H, 19F, and 11B NMR spectroscopy, solid state IR spectroscopy, elemental analysis, and X-ray crystallography. Figure 6: Molecular structure of PPN2 Ru(CF3bpy)(CNBCF)4. Thermal ellipsoids set at 50% probability. Cations, hydrogen and fluorine atoms, and solvent molecules omitted for clarity. 53 On addition of the borane, there is negligible change in the C-N distances and only a small shortening (ca. 0.05 Å) of the Ru-C distances (Figure 6). This observation is in line with the trends observed on addition of BCF to ferricyanide,23 and likely results from a balancing of the bond-lengthening effect of N-donation to the borane and the bond-shortening effect of increased backbonding from Ru to the more acidic isocyanoborate. Crystallization of the related heteroleptic borane adducts has been stymied by their high solubility,26,29 so more direct comparisons are not currently possible. Presumably due to steric crowding, the axial isocyanoborate ligands bow significantly (Ru-C-N bond angle 170°) over the plane of the bipyridine ligand, while those in the plane of the bipyridine remain close to linear. However, the crystal structure of PPN[Fe(phen)(CN-BPh3)4] does not display the same bowing effect (Ru-C-N = 176°), so there may be an electronic or crystal packing effect at play. Figure 7: IR spectrum of PPN2Ru(CF3bpy)(CN-BCF)4 with CN stretches highlighted in inset. 54 The C-N stretches in [Ru(CF3bpy)(CN-BCF)4]2- are shifted to much higher frequency (> 100 cm-1, Figure 7). This observation, which indicates that the C-N bond is strengthened by coordination of the borane, is also in line with the shifts observed in ferricyanide23 and other heteroleptic Ru complexes.26,29 Figure 8: UV-Vis spectra for PPN2Ru(CF3bpy)(CNBCF)4 in DCM (blue solid trace) and MeCN (orange broken trace). Addition of the boranes to [Ru(CF3bpy)(CN)4]2- induces a large blueshift in the optical absorption maximum, as the stronger Lewis acidity of BCF relative to water induces lowers the energy of the Ru- CF3 bpy orbitals, resulting in a blueshift in MeCN of the lowest-energy MLCT by nearly 8500 cm-1. The boronated complex displays solvatochromism (Figure 8), with a slightly redshifted and split MLCT in DCM, indicating there is still a dipole in the ground state. [Ru(CF3bpy)(CN-BCF)4]2- is also brightly emissive at 545 nm, with a long 55 excited-state lifetime of 3.4 µs and high quantum yield of 14.4%, and is photostable for weeks in solution under room lights. Figure 9: Cyclic voltammagram of 2.3 mM PPN2 Ru(CF3bpy)(CN-BCF)4 in 0.2 M Bu4NPF6-supported acetonitrile. Working electrode: glassy carbon. Counter electrode: Pt wire. Electrochemically, boronation with BCF induces a large anodic shift of 1.58 V in the potential of the Ru2+/3+ couple along with a 390 mV anodic shift of the CF3bpy0/·couple (Figure 9), comparable to the shifts observed for the parent bpy complex.26,29 While the peak current ratio for the CF3bpy0/·- remains near-unity, the peak-to-peak separation increases with increasing scan rate, indicating that the electron transfer is reversible but slow on the timescale of the scan rates used. The heterogeneous chargetransfer rate constant (k0) determined by Nicholson analysis (see Figure S5) of the appropriate variable scan rate data is 0.009 cm s-1. The peak current ratios for the 56 Ru2+/3+ couple deviate significantly from unity (average for all scan rates measured = 0.79) and decreases as the scan rate decreases, indicating a loss of reversibility attributable to an EC mechanism. Because the Ru2+/3+ couple occurs very near the edge of the stability window for Bu4NPF6-supported MeCN, it is impossible to determine whether this electrochemical irreversibility is inherent to PPN2 Ru(CF3bpy)(CN-BCF)4 or a result of solvent or supporting electrolyte decomposition. Figure 10: Top: room temperature absorption and emission data for [Ru(CF3bpy)(CN-BCF)4]2- in acetonitrile. Bottom: Modified Latimer diagram with potentials given in V vs. Fc+/0. 57 Combining the electrochemical and photophysical data, a modified Latimer diagram can be constructed (Figure 10) to estimate the excited-state redox potentials for [Ru(CF3bpy)(CN-BCF)4]2-. [Ru(CF3bpy)(CN-BCF)4]2- is expected to be a strong excited-state oxidant and modest excited state reductant, with an excited state oxidation potential comparable to [Ru(bpz)3]2+.34 Conclusion A new member of the [Ru(diimine)(CN)4]2- has been synthesized using the CF3bpy ligand, and it displays spectroscopic properties expected for an electron-withdrawing diimine. Notably, the library of [Ru(diimine)(CN)4]2- complexes with electronwithdrawing diimine ligands is currently limited to bis(diazines) and HOOCbpy. [Ru(CF3bpy)(CN)4]2- represents an addition to this library that is nonreactive to protons, which may be desirable for certain applications. The borane adduct [Ru(CF3bpy)(CN-BCF)4]2- has also been synthesized, and it represents an important step toward high voltage symmetric redox flow battery electrolytes with a voltage difference of 3.2 V. While the Ru2+/3+ couple occurs too close to the edge of the solvent stability window to be useful as a flow battery electrolyte, the enhanced stability of the CF3bpy0/- couple indicates that a different isocyanoborato complex of CF3bpy such as Ru(CF3bpy)2(CN-BCF)2 might be able to achieve the right balance of properties. [Ru(CF3bpy)(CN-BCF)4]2- also has luminescence properties that suggest it may be a useful photoredox catalyst. With 1 V of oxidizing power vs. Fc+/0, it may be a competent catalyst for photooxidations that currently utilize [Ru(bpz)3]2+ or [Ir[dF(CF3)ppy]2(dtbbpy)]+ as catalysts. 58 References (1) Bignozzi, C. A.; Chiorboli, C.; Indelli, M. T.; Rampi Scandola, M. A.; Varani, G.; Scandola, F. 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Generation of Powerful Tungsten Reductants by Visible Light Excitation. J. Am. Chem. Soc. 2013, 135 (29), 10614–10617. https://doi.org/10.1021/ja4047119. (40) Suzuki, K.; Kobayashi, A.; Kaneko, S.; Takehira, K.; Yoshihara, T.; Ishida, H.; Shiina, Y.; Oishi, S.; Tobita, S. Reevaluation of Absolute Luminescence Quantum Yields of Standard Solutions Using a Spectrometer with an Integrating Sphere and a BackThinned CCD Detector. Phys. Chem. Chem. Phys. 2009, 11 (42), 9850–9860. https://doi.org/10.1039/B912178A. (41) Crosby, G. A.; Demas, J. N. Measurement of Photoluminescence Quantum Yields. Review. J. Phys. Chem. 1971, 75 (8), 991–1024. https://doi.org/10.1021/j100678a001. 64 Methods General Considerations Potassium hexacyanoruthenate(II) was synthesized by a known procedure35. 4,4’trifluoromethyl-2,2’-bipyridine (CF3bpy, Strem), bis(triphenylphosphine)iminium chloride (PPNCl, Millipore Sigma), and tris(pentafluorophenyl)borane (BCF, TCI) were used as received. NMR spectra were collected on a Varian 400 MHz spectrometer ( -visible spectra were collected on a Cary 50 Bio or Cary 500 spectrometer. Solid-state infrared spectra were collected on a Thermo Scientific Nicolet iS5 FT-IR spectrometer with an iD5 ATR diamond. Synthesis & Characterization PPN2Ru(CF3bpy)(CN)4 K2Ru(CF3bpy)(CN)4 was synthesized with a modified version of the procedure published by Jiwan.30 To a boiling solution of K4Ru(CN)6 (400 mg, .908 mmol) and CF3 bpy (305 mg, 1.04 mmol) in 50 mL 1:1 methanol:water was added 400 L 3.6 N H2SO4 (pH 4). The solution was refluxed for 24 h, over which time it slowly turned red, then cooled to room temperature and neutralized. Excess CF3bpy was removed by filtration and the solvent was removed. The remaining residue was purified by gel-filtration chromatography on a Sephadex G-15 column. Elution with water gave a main orange band free of excess K4Ru(CN)6. The main fraction was dried under vacuum to give K2Ru(CF3bpy)(CN)4, yield 30%. The cation was exchanged by precipitation from concentrated aqueous solution with a saturated solution of PPNCl (307 mg, .535 mmol in 20 mL water). The resulting brick-red precipitate was collected by filtration and dried in a desiccator or under vacuum until it turned green, yield 326 mg (25%). Single crystals suitable for X-ray diffraction analysis were grown by slow evaporation from DCM solution. 1H NMR (400 MHz, CD2Cl2): 65 10.02 (d, J = 8 Hz, 2H, 6,6’-H), 8.12 (s, 2H, 3,3’-H), 7.69-7.65 (m, 24H, PPN), 7.527.44 (m, 36H, PPN), 7.40 (d, J = 8 Hz, 2H, 5,5’-H). 19F NMR (CD2Cl2): -64.71. IR (cm-1, CN stretches) 2062, 2090. Anal. Calcd for C88H66F6N8P4Ru: C, 67.13; H, 4.23; N, 7.12. Found: C, 64.21; H, 4.28; N, 5.55. PPN2Ru(CF3bpy)(CN-BCF)4 In a nitrogen-filled glovebox, PPN2Ru(CF3bpy)(CN)4 (100 mg, 0.0637 mmol) and excess BCF (133 mg, 0.261 mmol) were each dissolved in minimal DCM. The two solutions were combined, causing a rapid color change from green to red to yellow. The solution was stirred for 1 h, then dried under vacuum. The resulting luminescent yellow solid was washed 3 x 10 mL hexanes, then dried thoroughly under vacuum. The resulting air-stable material was then further purified by flash chromatography on silica gel (eluent gradient from 100% hexanes to 90% dichloromethane in hexanes), affording 131 mg yellow product (0.0362 mmol, 56% yield). Single crystals suitable for X-ray diffraction analysis were grown from a saturated ethanol solution at –25°C. 1H NMR (400 MHz, CD2Cl2): 9.22 (d, J = 4 Hz, 2H, 6,6’-H), 8.29 (s, 2H, 3,3’-H), 7.65-7.59 (m, 14H, PPN + 5,5’-H), 7.51-7.40 (m, 48H, PPN). 19 F NMR (CD2Cl2): -65.48 (s, 6F, CF3), -134.54 (dd, 12F, o-F), -135.00 (dd, 12F, o-F), -161.57 (t, 6F, p-F), -162.03 (t, 6F, p-F), -167.01 (td, 12F, m-F), -167.29 (td, 12F, m-F). 11B NMR (CD2Cl2): -14.09. IR (cm-1, CN stretches) 2171, 2216. Anal. Calcd for C160H66F66N8P4Ru: C, 53.05; H, 1.84; N, 3.09. Found: C, 51.69; H, 2.09; N, 2.76. Electrochemical Measurements Cyclic voltammagrams were taken in a nitrogen-filled glovebox with a Gamry Reference 600 potentiostat in a standard 3-electrode cell containing a 3 mm diameter glassy carbon working electrode, a 0.01 M Ag+/0 in 0.1 M TBAPF6/MeCN quasireference electrode, and a platinum wire counter electrode and compensated for 85% of the measured uncompensated resistance (Ru) value. 66 Diffusion coefficients were calculated from linear fits of plots of the peak current versus the square root of the scan rate using the Randles-Sevcik equation (Equation S1),36 where ip (A) is the peak current, n is the number of electrons transferred (1), F (C mol-1) is the Faraday constant, C (mol cm-1) is the bulk concentration of analyte, -1 ) is the scan rate, DO (cm2 s-1) is the diffusion coefficient of the oxidized analyte, R (J mol-1 K-1) is the ideal gas constant, and T (K) is the temperature. / = 0.446 (S1) The heterogeneous electron transfer rate constant (k0) for the CF3bpy0/·- couple of PPN2Ru(CF3bpy)(CN -BCF)4 was determined using Nicholson’s kinetic parameter 37 38 along wi (Equations S2 and S3). / = (S2) = .06288 + .0021 (S3) 1 0.017 -to-peak separation. For sufficiently fast scan rates with respect to -1/2 where become linear, and k0 may be calculated from the slope. For the other electrochemical couples observed, the scan rates used, and would have required very high (> 3 V/s) scan rates for this analysis. Photophysical Measurements Steady-state and time-resolved spectroscopic measurements were carried out in the Beckman Institute Laser Resource Center (California Institute of Technology) using methods described previously.39 67 PL) were measured by comparison of deaerated, optically dilute solutions of the molecule of interest to [Ru(bpy)3](PF6)2 in aerated and deaerated 40 PL = 0.018 for aerated solutions and 0.095 for aerated solutions ) according to Equation S4.41 = (S4) Subscript “ref” refers to the reference solutions, A are the absorbances at the exciting wavelength (450 nm for all measurements), I are the integrated emission intensities, and are the refractive indices of the solvents used. Absorption measurements were taken before and after emission spectra to ensure there was no photodecomposition. Emission spectra were taken twice with different integration times to ensure there were no significant differences. The resulting luminescence decay traces were fitted as an exponential decay to determine the excited state lifetimes ( ). 68 Supporting Data Figure S1: Randles-Sevcik plot for PPN2Ru(CF3bpy)(CN)4; D = 5.7 x 10-6 cm2 s-1. Figure S2: Variable scan rate cyclic voltammagrams for PPN2Ru(CF3bpy)(CN)4. 33 mM PPN2 Ru(CF3bpy)(CN)4 in 0.2 M Bu4NPF6-supported acetonitrile. Working electrode: glassy carbon. Counter electrode: Pt wire. 69 Figure S3: Randles-Sevcik plot for PPN2Ru(CF3bpy)(CN-BCF)4; D = 7.4 x 10-6 cm2 s-1 (top), 2.4 x 10-6 cm2 s-1 (bottom). Figure S4: Variable scan rate cyclic voltammetry of PPN2Ru(CF3bpy)(CN-BCF)4. . 2.3 mM PPN2 Ru(CF3bpy)(CN-BCF)4 in 0.2 M Bu4NPF6-supported acetonitrile. Working electrode: glassy carbon. Counter electrode: Pt wire. 70 0.8 0.7 y = 9.167E-03x - 7.070E-02 R² = 9.832E-01 0.6 0.5 0.4 0.3 0.2 0.1 0 0 10 20 30 40 50 (DnF /RT)-1/2 60 70 Figure S5: Nicholson analysis of the CF3bpy0/·- couple of PPN2Ru(CF3bpy)(CN-BCF)4, with a slope of k0. Figure S6: Steady-state emission spectrum of aqueous K2Ru(CF3bpy)(CN)4 excited at 400 nm. 80 90 71 Table S1: Measurement of quantum PPN2Ru(CF3bpy)(CN-BCF)4. Sample A450 I Aerated 0.0747 yield for wrt ref sample 8.30 x105 0.018 0.132 0.1043 5.08 x106 0.095 0.159 Sample 1 0.0467 3.79 x106 - - Aerated 0.0743 1.10 x106 0.018 0.131 0.0961 6.43 x106 0.095 0.153 0.0464 5.00 x106 - - [Ru(bpy)3]2+ 1 Deaerated [Ru(bpy)3]2+ 1 [Ru(bpy)3]2+ 2 Deaerated [Ru(bpy)3]2+ 2 Sample 2 0.144 average Figure S7: Left, time-resolved luminescence data for PPN2Ru(CF3bpy)(CN-BCF)4. Right, linear fit to determine lifetime. The slope of the fit is the inverse of 72 Figure S8: Dilution series for molar absorptivity of [Ru(CF3bpy)(CN)4]2- (K salt in water, PPN salt in MeCN) and linear fits. All measurements in 5 mm cuvette. Extinction coefficients are 332 = 3660 M-1cm-1, 443 = 3170 M-1cm-1 in water and 414 = 6190 M-1cm-1, 589 = 3770 M-1cm-1 in MeCN. 73 Figure S9: Dilution series for molar absorptivity of PPN2Ru(CF3bpy)(CN-BCF)4 and linear fits. All measurements in 5 mm cuvette. Extinction coefficients are 315 = 1460 M-1cm-1, 395 = 958 M-1cm-1, 410 = 1020 M-1cm-1 in DCM and 320 = 3860 M-1cm-1, 393 = 4440 M1 cm-1 in MeCN. 74 19 Figure S10: F NMR PPN2Ru(CF3bpy)(CN)4 in CD2Cl2. spectrum of 75 1 Figure S11: H NMR spectrum of PPN2Ru(CF3bpy)(CN)4 in CD2Cl2. Peaks upfield of 3 ppm are attributable to water, trace solvents, and silicone grease. 76 Figure S12: 11B NMR spectrum of PPN2Ru(CF3bpy)(CNBCF)4 in CD2Cl2 acquired in a quartz NMR tube. 77 Figure S13: 19F NMR spectrum of PPN2Ru(CF3bpy)(CNBCF)4 in CD2Cl2 with insets showing detail of BCF peaks. 78 Figure S14: 1H NMR spectrum of PPN2Ru(CF3bpy)(CNBCF)4 in CD2Cl2. Peaks upfield of 2 ppm are attributable to water, pentane, and silicone grease.