Coordination-Induced N–H Bond Weakening in a Molybdenum Pyrrolidine Complex: Isotopic Labeling Provides Insight into the Pathway for H2 Evolution

Bezdek, Máté J.; Pelczer, István; Chirik, Paul J.

doi:10.1021/acs.organomet.0c00471

Coordination-Induced N–H Bond Weakening in a Molybdenum Pyrrolidine Complex: Isotopic Labeling Provides Insight into the Pathway for H₂ Evolution

Journal Article · Tue Aug 04 00:00:00 EDT 2020 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.0c00471· OSTI ID:1646975

^[1]; ^[2]; ^[2]

Princeton Univ., NJ (United States); Princeton University
Princeton Univ., NJ (United States)

The synthesis and characterization of a cationic molybdenum pyrrolidine complex is described that exhibits significant coordination-induced N–H bond weakening. Here, the N–H bond dissociation free energy (BDFE) of the coordinated pyrrolidine in [(^PhTpy)(PPh₂Me)₂Mo(NH(pyrr))][BArF²⁴] ([1-NH(pyrr)]⁺; PhTpy = 4'-Ph-2,2',6',2''-terpyridine, NH(pyrr) = pyrrolidine, ArF²⁴ = [C₆H₃-3,5-(CF₃)₂]₄) was determined to be between 41–51 kcal mol^-1 by thermochemical analysis and supported by a density functional theory (DFT) computed value of 48 kcal mol^-1. The complex [1-NH(pyrr)]⁺ underwent proton-coupled electron transfer (PCET) to 2,4,6-tri-tert-butylphenoxyl radical, as well as spontaneous H₂ evolution upon gentle heating to furnish the corresponding molybdenum pyrrolidide complex, [(^PhTpy)(PPh₂Me)₂Mo(N(pyrr))][BArF²⁴] ([1-N(pyrr)]⁺). Thermolysis of the deuterated isotopolog, [1-ND(pyrr)]⁺ still produced H₂ with concomitant incorporation of the isotopic label into the pyrrolidide ligand in the product [(1-N(pyrr-d_n)]⁺ (n = 0–2), consistent with an H₂ evolution pathway involving intramolecular H–H bond formation followed by an intermolecular product-forming PCET step. These observations provide context for understanding H₂ evolution in the nonclassical ammine complex [(^PhTpy)(PPh₂Me)₂Mo(NH₃)][BArF²⁴] ([1-NH₃]⁺) and are supported by DFT-computed reaction thermochemistry. Overall, these studies offer rare insight into the H₂ formation pathway in nonclassical amine complexes with N–H BDFEs below the thermodynamic threshold for H₂ evolution and inform the development of well-defined, thermody-namically potent PCET reagents.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0006498

OSTI ID:: 1646975

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 16 Vol. 39; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (80)

Elements of Molecular and Biomolecular Electrochemistry Savéant, Jean-Michel https://doi.org/10.1002/0471758078	book	January 2006
Water: The Ideal Hydrogen-Atom Source in Free-Radical Chemistry Mediated by TiIII and Other Single-Electron-Transfer Metals? Cuerva, Juan M.; Campaña, Araceli G.; Justicia, José Angewandte Chemie International Edition, Vol. 45, Issue 33 https://doi.org/10.1002/anie.200600831	journal	August 2006
Coordination-Number Dependence of Reactivity in an Imidoiron(III) Complex Eckert, Nathan A.; Vaddadi, Sridhar; Stoian, Sebastian Angewandte Chemie International Edition, Vol. 45, Issue 41 https://doi.org/10.1002/anie.200601927	journal	October 2006
H2O Activation for Hydrogen-Atom Transfer: Correct Structures and Revised Mechanisms Gansäuer, Andreas; Behlendorf, Maike; Cangönül, Asli Angewandte Chemie International Edition, Vol. 51, Issue 13 https://doi.org/10.1002/anie.201107556	journal	February 2012
Synthesis and Ligand Modification Chemistry of a Molybdenum Dinitrogen Complex: Redox and Chemical Activity of a Bis(imino)pyridine Ligand Margulieux, Grant W.; Turner, Zoë R.; Chirik, Paul J. Angewandte Chemie International Edition, Vol. 53, Issue 51 https://doi.org/10.1002/anie.201408725	journal	October 2014
Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer Bezdek, Máté J.; Chirik, Paul J. Angewandte Chemie International Edition, Vol. 57, Issue 8 https://doi.org/10.1002/anie.201708406	journal	January 2018
Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride-Proton Isomerism, and HER Reactivity Buss, Joshua A.; Hirahara, Masanari; Ueda, Yohei Angewandte Chemie International Edition, Vol. 57, Issue 50 https://doi.org/10.1002/anie.201808307	journal	November 2018
Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer Abbenseth, Josh; Delony, Daniel; Neben, Marc C. Angewandte Chemie International Edition, Vol. 58, Issue 19 https://doi.org/10.1002/anie.201901470	journal	May 2019
Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction Bhattacharya, Papri; Heiden, Zachariah M.; Chambers, Geoffrey M. Angewandte Chemie International Edition, Vol. 58, Issue 34 https://doi.org/10.1002/anie.201903221	journal	June 2019
Towards Catalytic Ammonia Oxidation to Dinitrogen: A Synthetic Cycle by Using a Simple Manganese Complex Keener, Megan; Peterson, Madeline; Hernández Sánchez, Raúl Chemistry - A European Journal, Vol. 23, Issue 48 https://doi.org/10.1002/chem.201703153	journal	August 2017
Hydrogen-Atom Transfer Reactions of Transition-Metal Hydrides Eisenberg, David C.; Norton, Jack R. Israel Journal of Chemistry, Vol. 31, Issue 1 https://doi.org/10.1002/ijch.199100006	journal	January 1991
Hydrogen Generation via Activation of X-H Bonds in Ammonia and Water by an Mo ^I Complex Bandeira, Nuno A. G.; Veiros, Luís F.; Bo, Carles ChemistrySelect, Vol. 2, Issue 34 https://doi.org/10.1002/slct.201701801	journal	December 2017
Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities Miller, David C.; Tarantino, Kyle T.; Knowles, Robert R. Topics in Current Chemistry, Vol. 374, Issue 3 https://doi.org/10.1007/s41061-016-0030-6	journal	May 2016
Molecular Catalysts for Water Oxidation Blakemore, James D.; Crabtree, Robert H.; Brudvig, Gary W. Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00122	journal	July 2015
Transition-Metal Hydride Radical Cations Hu, Yue; Shaw, Anthony P.; Estes, Deven P. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.5b00532	journal	February 2016
Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins Crossley, Steven W. M.; Obradors, Carla; Martinez, Ruben M. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00334	journal	June 2016
Homolytic N–H Activation of Ammonia: Hydrogen Transfer of Parent Iridium Ammine, Amide, Imide, and Nitride Species Scheibel, Markus G.; Abbenseth, Josh; Kinauer, Markus Inorganic Chemistry, Vol. 54, Issue 19 https://doi.org/10.1021/acs.inorgchem.5b00829	journal	July 2015
Terpyridine Molybdenum Dinitrogen Chemistry: Synthesis of Dinitrogen Complexes That Vary by Five Oxidation States Bezdek, Máté J.; Guo, Sheng; Chirik, Paul J. Inorganic Chemistry, Vol. 55, Issue 6 https://doi.org/10.1021/acs.inorgchem.6b00053	journal	March 2016
CO-Photolysis-Induced H-Atom Transfer from Mn ^I O–H Bonds Kadassery, Karthika J.; Sethi, Komal; Fanara, Paul M. Inorganic Chemistry, Vol. 58, Issue 7 https://doi.org/10.1021/acs.inorgchem.9b00322	journal	March 2019
Electrocatalytic Ammonia Oxidation Mediated by a Polypyridyl Iron Catalyst Zott, Michael D.; Garrido-Barros, Pablo; Peters, Jonas C. ACS Catalysis, Vol. 9, Issue 11 https://doi.org/10.1021/acscatal.9b03499	journal	September 2019
Understanding Hydrogen Atom Transfer: From Bond Strengths to Marcus Theory Mayer, James M. Accounts of Chemical Research, Vol. 44, Issue 1 https://doi.org/10.1021/ar100093z	journal	January 2011
Climbing Nitrogenase: Toward a Mechanism of Enzymatic Nitrogen Fixation Hoffman, Brian M.; Dean, Dennis R.; Seefeldt, Lance C. Accounts of Chemical Research, Vol. 42, Issue 5 https://doi.org/10.1021/ar8002128	journal	May 2009
Proton-Coupled Electron Transfer Huynh, My Hang V.; Meyer, Thomas J. Chemical Reviews, Vol. 107, Issue 11 https://doi.org/10.1021/cr0500030	journal	November 2007
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M. Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr100085k	journal	December 2010
Proton-Coupled Electron Flow in Protein Redox Machines Dempsey, Jillian L.; Winkler, Jay R.; Gray, Harry B. Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr100182b	journal	December 2010
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y. Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr100246c	journal	November 2010
Introduction: Proton-Coupled Electron Transfer Hammes-Schiffer, Sharon Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr100367q	journal	December 2010
Bond Activation and Catalysis by Ruthenium Pincer Complexes Gunanathan, Chidambaram; Milstein, David Chemical Reviews, Vol. 114, Issue 24 https://doi.org/10.1021/cr5002782	journal	November 2014
Electronic Structure and Reactivity of Isomeric Oxo-Mn(V) Porphyrins: Effects of Spin-State Crossing and p K _a Modulation De Angelis, Filippo; Jin, Ning; Car, Roberto Inorganic Chemistry, Vol. 45, Issue 10 https://doi.org/10.1021/ic060306s	journal	May 2006
Pnictogen-Hydride Activation by (silox) ₃ Ta (silox = ^t Bu ₃ SiO); Attempts to Circumvent the Constraints of Orbital Symmetry in N ₂ Activation Hulley, Elliott B.; Bonanno, Jeffrey B.; Wolczanski, Peter T. Inorganic Chemistry, Vol. 49, Issue 18 https://doi.org/10.1021/ic101147x	journal	September 2010
Formation of Dinitrogen by Oxidation of [(bpy) ₂ (NH ₃ )RuORu(NH ₃ )(bpy) ₂ ] ⁴⁺ Ishitani, Osamu; White, Peter S.; Meyer, Thomas J. Inorganic Chemistry, Vol. 35, Issue 8 https://doi.org/10.1021/ic9512643	journal	January 1996
Mechanism of a Directly Observed .beta.-Hydride Elimination Process of Iridium Alkoxo Complexes Blum, Ofer; Milstein, David Journal of the American Chemical Society, Vol. 117, Issue 16 https://doi.org/10.1021/ja00121a016	journal	April 1995
Acidity-oxidation-potential (AOP) values as estimates of relative bond dissociation energies and radical stabilities in dimethyl sulfoxide solution Bordwell, Frederick G.; Bausch, Mark J. Journal of the American Chemical Society, Vol. 108, Issue 8 https://doi.org/10.1021/ja00268a041	journal	April 1986
Proton-coupled electron transfer between [Ru(bpy)2(py)OH2]2+ and [Ru(bpy)2(py)O]2+. A solvent isotope effect (kH2O/kD2O) of 16.1 Binstead, Robert A.; Moyer, Bruce A.; Samuels, George J. Journal of the American Chemical Society, Vol. 103, Issue 10 https://doi.org/10.1021/ja00400a083	journal	May 1981
Hydrocarbon Oxidation by Bis-μ-oxo Manganese Dimers: Electron Transfer, Hydride Transfer, and Hydrogen Atom Transfer Mechanisms Larsen, Anna S.; Wang, Kun; Lockwood, Mark A. Journal of the American Chemical Society, Vol. 124, Issue 34, p. 10112-10123 https://doi.org/10.1021/ja020204a	journal	August 2002
Electron and Hydrogen-Atom Self-Exchange Reactions of Iron and Cobalt Coordination Complexes Yoder, Jeffrey C.; Roth, Justine P.; Gussenhoven, Emily M. Journal of the American Chemical Society, Vol. 125, Issue 9 https://doi.org/10.1021/ja0273905	journal	March 2003
Monomeric Mn III/II and Fe III/II Complexes with Terminal Hydroxo and Oxo Ligands: Probing Reactivity via O−H Bond Dissociation Energies Gupta, Rajeev; Borovik, A. S. Journal of the American Chemical Society, Vol. 125, Issue 43 https://doi.org/10.1021/ja030149l	journal	October 2003
Activation of C−H / H−H Bonds by Rhodium(II) Porphyrin Bimetalloradicals Cui, Weihong; Wayland, Bradford B. Journal of the American Chemical Society, Vol. 126, Issue 26 https://doi.org/10.1021/ja049291s	journal	July 2004
Imido Transfer from Bis(imido)ruthenium(VI) Porphyrins to Hydrocarbons: Effect of Imido Substituents, C−H Bond Dissociation Energies, and Ru ^VI/V Reduction Potentials Leung, Sarana Ka-Yan; Tsui, Wai-Man; Huang, Jie-Sheng Journal of the American Chemical Society, Vol. 127, Issue 47 https://doi.org/10.1021/ja0542789	journal	November 2005
Thermodynamics of Rhodium Hydride Reactions with CO, Aldehydes, and Olefins in Water: Organo-Rhodium Porphyrin Bond Dissociation Free Energies Fu, Xuefeng; Wayland, Bradford B. Journal of the American Chemical Society, Vol. 127, Issue 47 https://doi.org/10.1021/ja054548n	journal	November 2005
Understanding the Exceptional Hydrogen-Atom Donor Characteristics of Water in Ti ^III -Mediated Free-Radical Chemistry Paradas, Miguel; Campaña, Araceli G.; Jiménez, Tania Journal of the American Chemical Society, Vol. 132, Issue 36 https://doi.org/10.1021/ja105670h	journal	September 2010
Rapid C–H Bond Activation by a Monocopper(III)–Hydroxide Complex Donoghue, Patrick J.; Tehranchi, Jacqui; Cramer, Christopher J. Journal of the American Chemical Society, Vol. 133, Issue 44 https://doi.org/10.1021/ja207882h	journal	November 2011
Unravelling the Mechanism of the Asymmetric Hydrogenation of Acetophenone by [RuX ₂ (diphosphine)(1,2-diamine)] Catalysts Dub, Pavel A.; Henson, Neil J.; Martin, Richard L. Journal of the American Chemical Society, Vol. 136, Issue 9 https://doi.org/10.1021/ja411374j	journal	February 2014
Four-Coordinate Cobalt Pincer Complexes: Electronic Structure Studies and Ligand Modification by Homolytic and Heterolytic Pathways Semproni, Scott P.; Milsmann, Carsten; Chirik, Paul J. Journal of the American Chemical Society, Vol. 136, Issue 25 https://doi.org/10.1021/ja504334a	journal	June 2014
Trends in Ground-State Entropies for Transition Metal Based Hydrogen Atom Transfer Reactions Mader, Elizabeth A.; Manner, Virginia W.; Markle, Todd F. Journal of the American Chemical Society, Vol. 131, Issue 12 https://doi.org/10.1021/ja8081846	journal	April 2009
Concerted Proton−Electron Transfer in a Ruthenium Terpyridyl-Benzoate System with a Large Separation between the Redox and Basic Sites Manner, Virginia W.; Mayer, James M. Journal of the American Chemical Society, Vol. 131, Issue 29 https://doi.org/10.1021/ja902942g	journal	July 2009
C−H Bond Activation by a Ferric Methoxide Complex: A Model for the Rate-Determining Step in the Mechanism of Lipoxygenase Jonas, Robert T.; Stack, T. D. P. Journal of the American Chemical Society, Vol. 119, Issue 36 https://doi.org/10.1021/ja971503g	journal	September 1997
Thermodynamics of C−H Activation in Multiple Oxidation States: Comparison of Benzylic C−H Acidities and C−H Bond Dissociation Energies in the Isostructural 16−20-Electron Complexes [Fe ^x ^{(η ⁵ -C ₅ R ₅ )(η ⁶ -arene)] ⁿ ^{, x = 0−IV, R = H or Me, n = −1 to +3}} Trujillo, Hernando A.; Casado, Carmen M.; Ruiz, Jaime Journal of the American Chemical Society, Vol. 121, Issue 24 https://doi.org/10.1021/ja984101x	journal	June 1999
A Cyclometalated Resting State for a Reactive Molybdenum Amide: Favorable Consequences of β-Hydrogen Elimination Including Reductive Cleavage, Coupling, and Complexation Tsai, Yi-Chou; Johnson, Marc J. A.; Mindiola, Daniel J. Journal of the American Chemical Society, Vol. 121, Issue 44 https://doi.org/10.1021/ja9917464	journal	November 1999
Intrinsic Barriers for Electron and Hydrogen Atom Transfer Reactions of Biomimetic Iron Complexes Roth, Justine P.; Lovell, Scott; Mayer, James M. Journal of the American Chemical Society, Vol. 122, Issue 23 https://doi.org/10.1021/ja9941328	journal	June 2000
Determining Proton-Coupled Standard Potentials and X–H Bond Dissociation Free Energies in Nonaqueous Solvents Using Open-Circuit Potential Measurements Wise, Catherine F.; Agarwal, Rishi G.; Mayer, James M. Journal of the American Chemical Society, Vol. 142, Issue 24 https://doi.org/10.1021/jacs.0c01032	journal	May 2020
Ammonia Synthesis by Hydrogenolysis of Titanium–Nitrogen Bonds Using Proton Coupled Electron Transfer Pappas, Iraklis; Chirik, Paul J. Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/jacs.5b01047	journal	March 2015
Bond-Weakening Catalysis: Conjugate Aminations Enabled by the Soft Homolysis of Strong N–H Bonds Tarantino, Kyle T.; Miller, David C.; Callon, Ted A. Journal of the American Chemical Society, Vol. 137, Issue 20 https://doi.org/10.1021/jacs.5b03428	journal	May 2015
Proton-Coupled Electron Transfer in the Reduction of Arenes by SmI ₂ –Water Complexes Chciuk, Tesia V.; Flowers, Robert A. Journal of the American Chemical Society, Vol. 137, Issue 35 https://doi.org/10.1021/jacs.5b07518	journal	August 2015
Reaction Parameters Influencing Cobalt Hydride Formation Kinetics: Implications for Benchmarking H ₂ -Evolution Catalysts Elgrishi, Noémie; Kurtz, Daniel A.; Dempsey, Jillian L. Journal of the American Chemical Society, Vol. 139, Issue 1 https://doi.org/10.1021/jacs.6b10148	journal	December 2016
Ammonia Synthesis from a Pincer Ruthenium Nitride via Metal–Ligand Cooperative Proton-Coupled Electron Transfer Lindley, Brian M.; Bruch, Quinton J.; White, Peter S. Journal of the American Chemical Society, Vol. 139, Issue 15 https://doi.org/10.1021/jacs.7b01323	journal	April 2017
SmI ₂ (H ₂ O) _n Reduction of Electron Rich Enamines by Proton-Coupled Electron Transfer Kolmar, Scott S.; Mayer, James M. Journal of the American Chemical Society, Vol. 139, Issue 31 https://doi.org/10.1021/jacs.7b03667	journal	July 2017
Thermodynamics of Proton and Electron Transfer in Tetranuclear Clusters with Mn–OH ₂ /OH Motifs Relevant to H ₂ O Activation by the Oxygen Evolving Complex in Photosystem II Reed, Christopher J.; Agapie, Theodor Journal of the American Chemical Society, Vol. 140, Issue 34 https://doi.org/10.1021/jacs.8b06426	journal	July 2018
Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism Bezdek, Máté J.; Chirik, Paul J. Journal of the American Chemical Society, Vol. 140, Issue 42 https://doi.org/10.1021/jacs.8b08460	journal	September 2018
Cleavage of N–H Bond of Ammonia via Metal–Ligand Cooperation Enables Rational Design of a Conceptually New Noyori–Ikariya Catalyst Dub, Pavel A.; Matsunami, Asuka; Kuwata, Shigeki Journal of the American Chemical Society, Vol. 141, Issue 6 https://doi.org/10.1021/jacs.8b12961	journal	January 2019
Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation Chalkley, Matthew J.; Oyala, Paul H.; Peters, Jonas C. Journal of the American Chemical Society, Vol. 141, Issue 11 https://doi.org/10.1021/jacs.9b00193	journal	February 2019
Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and Proton-Coupled Electron Transfer Bruch, Quinton J.; Connor, Gannon P.; Chen, Chun-Hsing Journal of the American Chemical Society, Vol. 141, Issue 51 https://doi.org/10.1021/jacs.9b10031	journal	November 2019
Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH ₃ through Modification of the Hydrogen Atom Abstractor Dunn, Peter L.; Johnson, Samantha I.; Kaminsky, Werner Journal of the American Chemical Society, Vol. 142, Issue 7 https://doi.org/10.1021/jacs.9b13706	journal	January 2020
Acid−Base Equilibria in Nonpolar Media. 4. Extension of the Self-Consistent Basicity Scale in THF Medium. Gas-Phase Basicities of Phosphazenes Kaljurand, Ivari; Rodima, Toomas; Pihl, Aino The Journal of Organic Chemistry, Vol. 68, Issue 26 https://doi.org/10.1021/jo034537h	journal	December 2003
Effects of .pi.-Coordinated Transition-Metal Groups on Fluorene Acidities and Homolytic Bond Dissociation Enthalpies Zhang, Shizhong; Bordwell, Frederick G. Organometallics, Vol. 13, Issue 8 https://doi.org/10.1021/om00020a002	journal	August 1994
Theoretical Study of the Oxidative Addition of Ammonia to Various Unsaturated Low-Valent Transition Metal Species Macgregor, Stuart A. Organometallics, Vol. 20, Issue 9 https://doi.org/10.1021/om010044w	journal	April 2001
Effects of the Niobium(V) Center on the Energetics of Ligand-Centered Proton and Hydrogen Atom Transfer Reactions in Acyl and Alkoxide Complexes Kerr, Margaret E.; Zhang, Xian-Man; Bruno, Joseph W. Organometallics, Vol. 16, Issue 15 https://doi.org/10.1021/om970224z	journal	July 1997
Ruthenium-catalysed oxidative conversion of ammonia into dinitrogen Nakajima, Kazunari; Toda, Hiroki; Sakata, Ken Nature Chemistry, Vol. 11, Issue 8 https://doi.org/10.1038/s41557-019-0293-y	journal	July 2019
Molybdenum-catalysed ammonia production with samarium diiodide and alcohols or water Ashida, Yuya; Arashiba, Kazuya; Nakajima, Kazunari Nature, Vol. 568, Issue 7753 https://doi.org/10.1038/s41586-019-1134-2	journal	April 2019
The roles of the first and second coordination spheres in the design of molecular catalysts for H ₂ production and oxidation Rakowski DuBois, M.; DuBois, Daniel L. Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B801197B	journal	January 2009
Thermodynamics of benzylic C–H activation in 18- and 19-electron iron sandwich complexes: determination of pK _a values and bond dissociation energies Trujillo, Hernando A.; Casado, Carmen Maria; Astruc, Didier J. Chem. Soc., Chem. Commun., Issue 1 https://doi.org/10.1039/C39950000007	journal	January 1995
O–H and (CO)N–H bond weakening by coordination to Fe( ii ) Resa, Sandra; Millán, Alba; Fuentes, Noelia Dalton Transactions, Vol. 48, Issue 6 https://doi.org/10.1039/C8DT04689A	journal	January 2019
Ammonia for hydrogen storage: challenges and opportunities Klerke, Asbjørn; Christensen, Claus Hviid; Nørskov, Jens K. Journal of Materials Chemistry, Vol. 18, Issue 20 https://doi.org/10.1039/b720020j	journal	January 2008
The role of proton coupled electron transfer in water oxidation Gagliardi, Christopher J.; Vannucci, Aaron K.; Concepcion, Javier J. Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee03311a	journal	January 2012
Homogeneous electrocatalytic oxidation of ammonia to N ₂ under mild conditions Habibzadeh, Faezeh; Miller, Susanne L.; Hamann, Thomas W. Proceedings of the National Academy of Sciences, Vol. 116, Issue 8 https://doi.org/10.1073/pnas.1813368116	journal	January 2019
Metal-Hydrogen Bond Cleavage Reactions of Transition Metal Hydrides: Hydrogen Atom, Hydride, and Proton Transfer Reactions Bullock, R. Morris Comments on Inorganic Chemistry, Vol. 12, Issue 1 https://doi.org/10.1080/02603599108018617	journal	May 1991
Application of the Marcus Cross Relation to Hydrogen Atom Transfer Reactions Roth, J. P. Science, Vol. 294, Issue 5551 https://doi.org/10.1126/science.1066130	journal	December 2001
Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics Rittle, J.; Green, M. T. Science, Vol. 330, Issue 6006 https://doi.org/10.1126/science.1193478	journal	November 2010
Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex Bezdek, Máté J.; Guo, Sheng; Chirik, Paul J. Science, Vol. 354, Issue 6313 https://doi.org/10.1126/science.aag0246	journal	November 2016
Proton-Coupled Electron Transfer in Biology: Results from Synergistic Studies in Natural and Model Systems Reece, Steven Y.; Nocera, Daniel G. Annual Review of Biochemistry, Vol. 78, Issue 1 https://doi.org/10.1146/annurev.biochem.78.080207.092132	journal	June 2009

Similar Records

Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer

Journal Article · Tue Jan 30 19:00:00 EST 2018 · Angewandte Chemie (International Edition) · OSTI ID:1418864

Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer

Journal Article · Tue Jan 30 19:00:00 EST 2018 · Angewandte Chemie · OSTI ID:1418874

Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism

Journal Article · Wed Sep 26 20:00:00 EDT 2018 · Journal of the American Chemical Society · OSTI ID:1478323

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Hydrogen isotopes
Ligands
Molybdenum
Proton coupled electron transfer
Pyrrolidines

Coordination-Induced N–H Bond Weakening in a Molybdenum Pyrrolidine Complex: Isotopic Labeling Provides Insight into the Pathway for H2 Evolution

Citation Formats

References (80)

Similar Records

Related Subjects

Coordination-Induced N–H Bond Weakening in a Molybdenum Pyrrolidine Complex: Isotopic Labeling Provides Insight into the Pathway for H₂ Evolution