Elucidation of Marcus Relationships for Hydride Transfer Reactions Involving Transition Metal Hydrides

Kumar, Abhishek; Ertem, Mehmed Z.; Hazari, Nilay; Miller, Alexander J. M.

doi:10.1021/jacs.5c08248

Elucidation of Marcus Relationships for Hydride Transfer Reactions Involving Transition Metal Hydrides

Journal Article · Mon Aug 25 00:00:00 EDT 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5c08248· OSTI ID:2997742

^[1]; ^[2]; ^[1]; ^[3]

Yale Univ., New Haven, CT (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
University of North Carolina, Chapel Hill, NC (United States)

The rate of hydride transfer from three Ir hydride complexes of the type Cp*Ir(^Rbpy)H⁺ (Cp* = C₅Me₅; ^Rbpy = 4,4′-R-2,2′-bipyridine, R = OMe, H, CO₂Me) to six N-methylacridinium (^RAcr⁺) acceptors with electronically different substituents in the 2- or 2,7-positions were measured. Using the thermodynamic hydricity of the donors and the hydride affinity of the acceptors the thermodynamic driving forces for hydride transfer were determined. Brønsted plots, which correlate kinetic and thermodynamic hydricity, demonstrate distinct linear free energy relationships for each complex, with different Brønsted α values. Thus, at the same driving force hydride transfer from Cp*Ir(^OMebpy)H⁺ is faster than for Cp*Ir(bpy)H⁺ or Cp*Ir(^CO2Mebpy)H⁺. Experimental and computational analyses are consistent with a concerted hydride transfer mechanism for all Ir complexes. As the thermodynamic driving force increases an earlier transition state is observed and all transition states also include π-stacking interactions between the donor and acceptor, which likely contribute to the different α values. The experimental data fits well to the Marcus model, enabling the determination of reorganization energies (λ) that range from 58 to 69 kcal mol^-1. These are lower than λ values for hydride transfer reactions involving organic donors and acceptors. This work provides a rare example of the correlation of kinetic and thermodynamic hydricity using only experimental data and shows that hydride transfer reactions involving metal hydrides can follow Marcus theory. Furthermore, the findings offer insight into controlling metal-catalyzed hydride transfer reactions, which is valuable for designing improved systems for a range of transformations.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704; SC0014255

OSTI ID:: 2997742

Report Number(s):: BNL--229021-2025-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 36 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (119)

Selective Hydrogenation for Fine Chemicals: Recent Trends and New Developments Blaser, Hans-Ulrich; Malan, Christophe; Pugin, Benoît Advanced Synthesis & Catalysis, Vol. 345, Issue 12 https://doi.org/10.1002/adsc.200390000	journal	January 2003
Quantitatively Correlating the Effect of Ligand-Substituent Size in Asymmetric Catalysis Using Linear Free Energy Relationships Miller, Jeremie J.; Sigman, Matthew S. Angewandte Chemie International Edition, Vol. 47, Issue 4 https://doi.org/10.1002/anie.200704257	journal	January 2008
Transformation of Carbon Dioxide with Homogeneous Transition-Metal Catalysts: A Molecular Solution to a Global Challenge? Cokoja, Mirza; Bruckmeier, Christian; Rieger, Bernhard Angewandte Chemie International Edition, Vol. 50, Issue 37 https://doi.org/10.1002/anie.201102010	journal	August 2011
Catalytic Disproportionation of Formic Acid to Generate Methanol Miller, Alexander J. M.; Heinekey, D. Michael; Mayer, James M. Angewandte Chemie International Edition, Vol. 52, Issue 14 https://doi.org/10.1002/anie.201208470	journal	February 2013
Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem Angewandte Chemie International Edition, Vol. 55, Issue 26 https://doi.org/10.1002/anie.201507458	journal	May 2016
Hydroformylation. Fundamentals, Processes, and Applications in Organic Synthesis. By Armin Börner and Robert Franke. Clarke, Matthew L. Angewandte Chemie International Edition, Vol. 55, Issue 43 https://doi.org/10.1002/anie.201607967	journal	September 2016
Recent Advances in Catalytic Hydrosilylations: Developments beyond Traditional Platinum Catalysts Almeida, Leandro Duarte; Wang, Hongli; Junge, Kathrin Angewandte Chemie International Edition, Vol. 60, Issue 2 https://doi.org/10.1002/anie.202008729	journal	December 2020
Double Bond Isomerisation and Migration-New Playgrounds for Transition Metal-Catalysis Hilt, Gerhard ChemCatChem, Vol. 6, Issue 9 https://doi.org/10.1002/cctc.201402341	journal	July 2014
Reusable Catalysts for Hydroformylation‐Based Reactions Rodrigues, Fábio M. S.; Carrilho, Rui M. B.; Pereira, Mariette M. European Journal of Inorganic Chemistry, Vol. 2021, Issue 24 https://doi.org/10.1002/ejic.202100032	journal	May 2021
Tandem Arylation/Friedel–Crafts Reactions of o‐Acylanilines with Diaryliodonium Salts: A Modular Synthesis of Acridine Derivatives Pang, Xinlong; Lou, Zhenbang; Li, Ming European Journal of Organic Chemistry, Vol. 2015, Issue 15 https://doi.org/10.1002/ejoc.201500161	journal	April 2015
Reactivities of acridine compounds in hydride transfer reactions Lee, In‐Sook Han; Kil, Hyun Joo; Ji, Young Ran Journal of Physical Organic Chemistry, Vol. 20, Issue 7 https://doi.org/10.1002/poc.1182	journal	May 2007
Linear free energy relationships in heterogeneous catalysis I. Dealkylation of alkylbenzenes on cracking catalysts Mochida, I. Journal of Catalysis, Vol. 7, Issue 4 https://doi.org/10.1016/0021-9517(67)90167-4	journal	April 1967
Reorganization energies in benzene, naphthalene, and anthracene Klimkāns, Agris; Larsson, Sven Chemical Physics, Vol. 189, Issue 1 https://doi.org/10.1016/0301-0104(94)80004-9	journal	November 1994
Early transition metal hydride complexes: synthesis and reactivity Hoskin, A. Coordination Chemistry Reviews, Vol. 233-234 https://doi.org/10.1016/S0010-8545(02)00030-9	journal	November 2002
Transition metal hydrides as active intermediates in hydrogen transfer reactions Bäckvall, Jan-E Journal of Organometallic Chemistry, Vol. 652, Issue 1-2 https://doi.org/10.1016/S0022-328X(02)01316-5	journal	June 2002
Recent advances in the 18-electron complex transition metal hydrides of Ni, Fe, Co and Ru Humphries, Terry D.; Sheppard, Drew A.; Buckley, Craig E. Coordination Chemistry Reviews, Vol. 342 https://doi.org/10.1016/j.ccr.2017.04.001	journal	July 2017
Recent advances in homogeneous base-metal-catalyzed transfer hydrogenation reactions Baidilov, Daler; Hayrapetyan, Davit; Khalimon, Andrey Y. Tetrahedron, Vol. 98 https://doi.org/10.1016/j.tet.2021.132435	journal	October 2021
Biomimetic Metal-Free Hydride Donor Catalysts for CO₂ Reduction Ilic, Stefan; Gesiorski, Jonathan L.; Weerasooriya, Ravindra B. Accounts of Chemical Research, Vol. 55, Issue 6 https://doi.org/10.1021/acs.accounts.1c00708	journal	February 2022
Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts Bernskoetter, Wesley H.; Hazari, Nilay Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.7b00039	journal	February 2017
Isomerization of Allylbenzenes Hassam, Mohammad; Taher, Abu; Arnott, Gareth E. Chemical Reviews, Vol. 115, Issue 11 https://doi.org/10.1021/acs.chemrev.5b00052	journal	May 2015
CO ₂ Hydrogenation to Formate and Methanol as an Alternative to Photo- and Electrochemical CO ₂ Reduction Wang, Wan-Hui; Himeda, Yuichiro; Muckerman, James T. Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00197	journal	August 2015
The Golden Age of Transfer Hydrogenation Wang, Dong; Astruc, Didier Chemical Reviews, Vol. 115, Issue 13 https://doi.org/10.1021/acs.chemrev.5b00203	journal	June 2015
Thermodynamic Hydricity of Transition Metal Hydrides Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00168	journal	June 2016
Introduction: Metal Hydrides Norton, Jack R.; Sowa, John Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00441	journal	June 2016
Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K. Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00182	journal	October 2017
Hydride Transfer Reactions Catalyzed by Cobalt Complexes Ai, Wenying; Zhong, Rui; Liu, Xufang Chemical Reviews, Vol. 119, Issue 4 https://doi.org/10.1021/acs.chemrev.8b00404	journal	October 2018
Prediction of Kinetic Isotope Effects for Various Hydride Transfer Reactions Using a New Kinetic Model Shen, Guang-Bin; Xia, Ke; Li, Xiu-Tao The Journal of Physical Chemistry A, Vol. 120, Issue 11 https://doi.org/10.1021/acs.jpca.5b10135	journal	March 2016
New Way for Probing Bond Strength Klein, Johanna; Khartabil, Hassan; Boisson, Jean-Charles The Journal of Physical Chemistry A, Vol. 124, Issue 9 https://doi.org/10.1021/acs.jpca.9b09845	journal	February 2020
Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO ₂ Weerasooriya, Ravindra B.; Gesiorski, Jonathan L.; Alherz, Abdulaziz The Journal of Physical Chemistry Letters, Vol. 12, Issue 9 https://doi.org/10.1021/acs.jpclett.0c03662	journal	March 2021
Urea and Thiourea H-Bond Donating Catalysts for Ring-Opening Polymerization: Mechanistic Insights via (Non)linear Free Energy Relationships Pothupitiya, Jinal U.; Hewawasam, Rukshika S.; Kiesewetter, Matthew K. Macromolecules, Vol. 51, Issue 8 https://doi.org/10.1021/acs.macromol.8b00321	journal	April 2018
Carbon Dioxide Insertion into Rhenium Hydrides as a Probe for the Impact of Solvent on Linear Free Energy Relationships between Thermodynamic and Kinetic Hydricity Elsby, Matthew R.; Espinosa, Matthew R.; Ertem, Mehmed Z. Organometallics, Vol. 42, Issue 20 https://doi.org/10.1021/acs.organomet.3c00333	journal	October 2023
Catalytic Homogeneous Asymmetric Hydrogenation: Successes and Opportunities Seo, Chris S. G.; Morris, Robert H. Organometallics, Vol. 38, Issue 1 https://doi.org/10.1021/acs.organomet.8b00774	journal	December 2018
Thermodynamic Hydricity across Solvents: Subtle Electronic Effects and Striking Ligation Effects in Iridium Hydrides Brereton, Kelsey R.; Jadrich, Caleb N.; Stratakes, Bethany M. Organometallics, Vol. 38, Issue 16 https://doi.org/10.1021/acs.organomet.9b00278	journal	July 2019
Alkene Isomerization through Allylmetals as a Strategic Tool in Stereoselective Synthesis Massad, Itai; Marek, Ilan ACS Catalysis, Vol. 10, Issue 10 https://doi.org/10.1021/acscatal.0c01174	journal	April 2020
Distinct Mechanisms and Hydricities of Cp*Ir-Based CO ₂ Hydrogenation Catalysts in Basic Water Nijamudheen, A.; Kanega, Ryoichi; Onishi, Naoya ACS Catalysis, Vol. 11, Issue 9 https://doi.org/10.1021/acscatal.0c04772	journal	April 2021
Advances in Base-Metal-Catalyzed Alkene Hydrosilylation Du, Xiaoyong; Huang, Zheng ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b02990	journal	January 2017
Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO ₂ Reduction Waldie, Kate M.; Ostericher, Andrew L.; Reineke, Mark H. ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03396	journal	January 2018
Supramolecular Approaches To Control Activity and Selectivity in Hydroformylation Catalysis Nurttila, Sandra S.; Linnebank, Pim R.; Krachko, Tetiana ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.8b00288	journal	March 2018
Transient Species in the Stepwise Interconversion of NADH and NAD⁺ Gȩbicki, Jerzy; Marcinek, Andrzej; Zielonka, Jacek Accounts of Chemical Research, Vol. 37, Issue 6 https://doi.org/10.1021/ar030171j	journal	March 2004
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
Transition-Metal-Catalyzed Carbonylation Reactions of Olefins and Alkynes: A Personal Account Wu, Xiao-Feng; Fang, Xianjie; Wu, Lipeng Accounts of Chemical Research, Vol. 47, Issue 4 https://doi.org/10.1021/ar400222k	journal	February 2014
Industrial-Scale Synthesis and Applications of Asymmetric Hydrogenation Catalysts Johnson, Nicholas B.; Lennon, Ian C.; Moran, Paul H. Accounts of Chemical Research, Vol. 40, Issue 12 https://doi.org/10.1021/ar700114k	journal	December 2007
Catalysis and Linear Free Energy Relationships in Aspartic Proteases ^† Bjelic, Sinisa; Åqvist, Johan Biochemistry, Vol. 45, Issue 25 https://doi.org/10.1021/bi060131y	journal	June 2006
The search for larger and more weakly coordinating anions Strauss, Steven H. Chemical Reviews, Vol. 93, Issue 3 https://doi.org/10.1021/cr00019a005	journal	May 1993
Applied Hydroformylation Franke, Robert; Selent, Detlef; Börner, Armin Chemical Reviews, Vol. 112, Issue 11 https://doi.org/10.1021/cr3001803	journal	August 2012
Dehydrogenation as a Substrate-Activating Strategy in Homogeneous Transition-Metal Catalysis Dobereiner, Graham E.; Crabtree, Robert H. Chemical Reviews, Vol. 110, Issue 2 https://doi.org/10.1021/cr900202j	journal	February 2010
Electrochemical Solvent Reorganization Energies in the Framework of the Polarizable Continuum Model Ghosh, Soumya; Horvath, Samantha; Soudackov, Alexander V. Journal of Chemical Theory and Computation, Vol. 10, Issue 5 https://doi.org/10.1021/ct500051e	journal	April 2014
Marcus theory in organic chemistry. Mechanisms of electron and proton transfers from aromatics and their cation radicals Schlesener, C. J.; Amatore, C.; Kochi, J. K. The Journal of Physical Chemistry, Vol. 90, Issue 16 https://doi.org/10.1021/j100407a049	journal	July 1986
Application of the Marcus equation to methyl transfers Lewis, Edward S. The Journal of Physical Chemistry, Vol. 90, Issue 16 https://doi.org/10.1021/j100407a050	journal	July 1986
Phenomenological manifestations of large-curvature tunneling in hydride-transfer reactions Kreevoy, Maurice M.; Ostovic, Drazen; Truhlar, Donald G. The Journal of Physical Chemistry, Vol. 90, Issue 16 https://doi.org/10.1021/j100407a052	journal	July 1986
An experimentally based family of potential energy surfaces for hydride transfer between NAD+ analogs Kim, Yongho; Truhlar, Donald G.; Kreevoy, Maurice M. Journal of the American Chemical Society, Vol. 113, Issue 21 https://doi.org/10.1021/ja00021a002	journal	October 1991
The Marcus theory of the reactions of quinolinium ions with borohydride and hydroxide Kim, Duckhee; Lee, In Sook Han; Kreevoy, Maurice M. Journal of the American Chemical Society, Vol. 112, Issue 5 https://doi.org/10.1021/ja00161a037	journal	February 1990
Electron-transfer reactions of radical anions: do they follow outer- or inner-sphere mechanisms? Eberson, Lennart; Shaik, Sason S. Journal of the American Chemical Society, Vol. 112, Issue 11 https://doi.org/10.1021/ja00167a055	journal	May 1990
Structure sensitivity of the Marcus .lambda. for hydride transfer between NAD+ analogs Kreevoy, Maurice M.; Ostovic, Drazen.; Lee, In Sook Han. Journal of the American Chemical Society, Vol. 110, Issue 2 https://doi.org/10.1021/ja00210a036	journal	January 1988
Estimation of inner shell Marcus terms for amino nitrogen compounds by molecular orbital calculations Nelsen, Stephen F.; Blackstock, Silas C.; Kim, Yaesil Journal of the American Chemical Society, Vol. 109, Issue 3 https://doi.org/10.1021/ja00237a007	journal	February 1987
Long-range photoinduced through-bond electron transfer and radiative recombination via rigid nonconjugated bridges: distance and solvent dependence Oevering, Henk; Paddon-Row, Michael N.; Heppener, Marc Journal of the American Chemical Society, Vol. 109, Issue 11 https://doi.org/10.1021/ja00245a014	journal	May 1987
Application of Marcus theory to metal ion catalyzed group transfer reactions Leussing, Daniel L.; Emly, Mark Journal of the American Chemical Society, Vol. 106, Issue 2 https://doi.org/10.1021/ja00314a043	journal	January 1984
Marcus theory of a perpendicular effect on .alpha. for hydride transfer between NAD+ analogs Kreevoy, Maurice M.; Lee, In Sook Han Journal of the American Chemical Society, Vol. 106, Issue 9 https://doi.org/10.1021/ja00321a011	journal	May 1984
Kinetics and mechanism of aromatic oxidative substitutions via electron transfer. Application of Marcus theory to organic processes in the endergonic region Schlesener, C. J.; Amatore, C.; Kochi, J. K. Journal of the American Chemical Society, Vol. 106, Issue 12 https://doi.org/10.1021/ja00324a027	journal	June 1984
Isotope effects on hydride transfer between NAD+ analogs Ostovic, Drazen; Roberts, Roger M. G.; Kreevoy, Maurice M. Journal of the American Chemical Society, Vol. 105, Issue 26 https://doi.org/10.1021/ja00364a026	journal	December 1983
Theoretical studies of SN2 transition states. 2. Intrinsic barriers, rate-equilibrium relationships, and the Marcus equation Wolfe, Saul; Mitchell, David John; Schlegel, H. Bernhard Journal of the American Chemical Society, Vol. 103, Issue 25 https://doi.org/10.1021/ja00415a069	journal	December 1981
Rate-Equilibrium Relationships in Hydride Transfer Reactions: The Role of Intrinsic Barriers Würthwein, Ernst-Ulrich; Lang, Gabriele; Schappele, Ludwig H. Journal of the American Chemical Society, Vol. 124, Issue 15 https://doi.org/10.1021/ja0121540	journal	April 2002
Hydricities of BzNADH, C ₅ H ₅ Mo(PMe ₃ )(CO) ₂ H, and C ₅ Me ₅ Mo(PMe ₃ )(CO) ₂ H in Acetonitrile Ellis, William W.; Raebiger, James W.; Curtis, Calvin J. Journal of the American Chemical Society, Vol. 126, Issue 9 https://doi.org/10.1021/ja038567d	journal	March 2004
Nonperfect Synchronization of Reaction Center Rehybridization in the Transition State of the Hydride Transfer Catalyzed by Dihydrofolate Reductase Pu, Jingzhi; Ma, Shuhua; Garcia-Viloca, Mireia Journal of the American Chemical Society, Vol. 127, Issue 42 https://doi.org/10.1021/ja054170t	journal	September 2005
Theoretical Analysis of Proton Relays in Electrochemical Proton-Coupled Electron Transfer Auer, Benjamin; Fernandez, Laura E.; Hammes-Schiffer, Sharon Journal of the American Chemical Society, Vol. 133, Issue 21 https://doi.org/10.1021/ja201560v	journal	June 2011
Thermodynamic and Kinetic Hydricity of Ruthenium(II) Hydride Complexes Matsubara, Yasuo; Fujita, Etsuko; Doherty, Mark D. Journal of the American Chemical Society, Vol. 134, Issue 38 https://doi.org/10.1021/ja302937q	journal	September 2012
Photoswitchable Hydride Transfer from Iridium to 1-Methylnicotinamide Rationalized by Thermochemical Cycles Barrett, Seth M.; Pitman, Catherine L.; Walden, Andrew G. Journal of the American Chemical Society, Vol. 136, Issue 42 https://doi.org/10.1021/ja508762g	journal	October 2014
Hydrogen Atom Transfer Reactions of a Ruthenium Imidazole Complex: Hydrogen Tunneling and the Applicability of the Marcus Cross Relation Wu, Adam; Mayer, James M. Journal of the American Chemical Society, Vol. 130, Issue 44 https://doi.org/10.1021/ja805067h	journal	November 2008
Marcus Theory of a Parallel Effect on α for Hydride Transfer Reaction between NAD ⁺ Analogues Lee, In-Sook Han; Jeoung, Eun Hee; Kreevoy, Maurice M. Journal of the American Chemical Society, Vol. 119, Issue 11 https://doi.org/10.1021/ja963768l	journal	March 1997
Hydride Transfer Reactions of Transition Metal Hydrides: Kinetic Hydricity of Metal Carbonyl Hydrides Cheng, Tan-Yun; Brunschwig, Bruce S.; Bullock, R. Morris Journal of the American Chemical Society, Vol. 120, Issue 50 https://doi.org/10.1021/ja9820036	journal	December 1998
Thermodynamic and Kinetic Studies of Hydride Transfer for a Series of Molybdenum and Tungsten Hydrides Sarker, Niladri; Bruno, Joseph W. Journal of the American Chemical Society, Vol. 121, Issue 10 https://doi.org/10.1021/ja982017b	journal	March 1999
Steric Control of Electron Transfer. Changeover from Outer-Sphere to Inner-Sphere Mechanisms in Arene/Quinone Redox Pairs Hubig, Stephan M.; Rathore, Rajendra; Kochi, Jay K. Journal of the American Chemical Society, Vol. 121, Issue 4 https://doi.org/10.1021/ja9831002	journal	January 1999
Isotope Effects on Hydride Transfer Reactions from Transition Metal Hydrides to Trityl Cation. An Inverse Isotope Effect for a Hydride Transfer Cheng, Tan-Yun; Bullock, R. Morris Journal of the American Chemical Society, Vol. 121, Issue 13 https://doi.org/10.1021/ja983448x	journal	April 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
Bimodal Evans–Polanyi Relationships in Hydrogen Atom Transfer from C(sp³)–H Bonds to the Cumyloxyl Radical. A Combined Time-Resolved Kinetic and Computational Study Salamone, Michela; Galeotti, Marco; Romero-Montalvo, Eduardo Journal of the American Chemical Society, Vol. 143, Issue 30 https://doi.org/10.1021/jacs.1c05566	journal	July 2021
Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides Espinosa, Matthew R.; Ertem, Mehmed Z.; Barakat, Mariam Journal of the American Chemical Society, Vol. 144, Issue 39 https://doi.org/10.1021/jacs.2c07192	journal	September 2022
Thermodynamic and Kinetic Activity Descriptors for the Catalytic Hydrogenation of Ketones Chirila, Andrei; Hu, Yiqin; Linehan, John C. Journal of the American Chemical Society, Vol. 146, Issue 10 https://doi.org/10.1021/jacs.3c13876	journal	March 2024
Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium Pitman, Catherine L.; Brereton, Kelsey R.; Miller, Alexander J. M. Journal of the American Chemical Society, Vol. 138, Issue 7 https://doi.org/10.1021/jacs.5b12363	journal	February 2016
Theoretical Study of C–H Bond Cleavage via Concerted Proton-Coupled Electron Transfer in Fluorenyl-Benzoates Sayfutyarova, Elvira R.; Goldsmith, Zachary K.; Hammes-Schiffer, Sharon Journal of the American Chemical Society, Vol. 140, Issue 46 https://doi.org/10.1021/jacs.8b10461	journal	November 2018
Rate–Driving Force Relationships in the Multisite Proton-Coupled Electron Transfer Activation of Ketones Qiu, Guanqi; Knowles, Robert R. Journal of the American Chemical Society, Vol. 141, Issue 6 https://doi.org/10.1021/jacs.8b13451	journal	January 2019
Transition State Asymmetry in C–H Bond Cleavage by Proton-Coupled Electron Transfer Darcy, Julia W.; Kolmar, Scott S.; Mayer, James M. Journal of the American Chemical Society, Vol. 141, Issue 27 https://doi.org/10.1021/jacs.9b04303	journal	June 2019
Understanding the Individual and Combined Effects of Solvent and Lewis Acid on CO ₂ Insertion into a Metal Hydride Heimann, Jessica E.; Bernskoetter, Wesley H.; Hazari, Nilay Journal of the American Chemical Society, Vol. 141, Issue 26 https://doi.org/10.1021/jacs.9b05192	journal	May 2019
Strategies for Enhancing the Rate Constant of C–H Bond Cleavage by Concerted Proton-Coupled Electron Transfer Sayfutyarova, Elvira R.; Lam, Yan-Choi; Hammes-Schiffer, Sharon Journal of the American Chemical Society, Vol. 141, Issue 38 https://doi.org/10.1021/jacs.9b06849	journal	August 2019
Reactivities of Five-Membered Heterocycles in Hydride Transfer Reactions Lee, In-Sook Han; Jeoung, Eun Hee The Journal of Organic Chemistry, Vol. 63, Issue 21 https://doi.org/10.1021/jo980707s	journal	September 1998
Reinterpretation of the Brønsted α for Redox Reactions Based on the Effect of Substituents on Hydride Transfer Reaction Rates between NAD⁺ Analogues Lee, In-Sook Han; Ji, Young Ran; Jeoung, Eun Hee The Journal of Physical Chemistry A, Vol. 110, Issue 11 https://doi.org/10.1021/jp056745e	journal	February 2006
Transition State Barriers in Multidimensional Marcus Theory Zwickl, Jill; Shenvi, Neil; Schmidt, J. R. The Journal of Physical Chemistry A, Vol. 112, Issue 42 https://doi.org/10.1021/jp805065g	journal	October 2008
Primary Kinetic Isotope Effects on Hydride Transfer from Heterocyclic Compounds to NAD⁺ Analogues Kil, Hyun Joo; Lee, In-Sook Han The Journal of Physical Chemistry A, Vol. 113, Issue 40 https://doi.org/10.1021/jp905937x	journal	September 2009
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model Barone, Vincenzo; Cossi, Maurizio The Journal of Physical Chemistry A, Vol. 102, Issue 11 https://doi.org/10.1021/jp9716997	journal	March 1998
Simple Marcus-Theory-Type Model for Hydrogen-Atom Transfer/Proton-Coupled Electron Transfer Mayer, James M. The Journal of Physical Chemistry Letters, Vol. 2, Issue 12 https://doi.org/10.1021/jz200021y	journal	May 2011
Remote functionalization through alkene isomerization Vasseur, Alexandre; Bruffaerts, Jeffrey; Marek, Ilan Nature Chemistry, Vol. 8, Issue 3 https://doi.org/10.1038/nchem.2445	journal	February 2016
Earth-abundant transition metal catalysts for alkene hydrosilylation and hydroboration Obligacion, Jennifer V.; Chirik, Paul J. Nature Reviews Chemistry, Vol. 2, Issue 5 https://doi.org/10.1038/s41570-018-0001-2	journal	April 2018
Homogeneous hydrogenation of carbon dioxide to methanol Li, Yu-Nong; Ma, Ran; He, Liang-Nian Catal. Sci. Technol., Vol. 4, Issue 6 https://doi.org/10.1039/C3CY00564J	journal	January 2014
Well-defined transition metal hydrides in catalytic isomerizations Larionov, Evgeny; Li, Houhua; Mazet, Clément Chemical Communications, Vol. 50, Issue 69 https://doi.org/10.1039/C4CC02399D	journal	January 2014
Recycling of carbon dioxide to methanol and derived products – closing the loop Goeppert, Alain; Czaun, Miklos; Jones, John-Paul Chem. Soc. Rev., Vol. 43, Issue 23 https://doi.org/10.1039/C4CS00122B	journal	January 2014
Hydrosilylation reaction of olefins: recent advances and perspectives Nakajima, Y.; Shimada, S. RSC Advances, Vol. 5, Issue 26 https://doi.org/10.1039/C4RA17281G	journal	January 2015
Electronic effects on the catalytic disproportionation of formic acid to methanol by [Cp*Ir ^III (R-bpy)Cl]Cl complexes Sasayama, A. F.; Moore, C. E.; Kubiak, C. P. Dalton Transactions, Vol. 45, Issue 6 https://doi.org/10.1039/C5DT04606H	journal	January 2016
Thermodynamic and kinetic hydricities of metal-free hydrides Ilic, Stefan; Alherz, Abdulaziz; Musgrave, Charles B. Chemical Society Reviews, Vol. 47, Issue 8 https://doi.org/10.1039/C7CS00171A	journal	January 2018
Acceleration of CO ₂ insertion into metal hydrides: ligand, Lewis acid, and solvent effects on reaction kinetics Heimann, Jessica E.; Bernskoetter, Wesley H.; Hazari, Nilay Chemical Science, Vol. 9, Issue 32 https://doi.org/10.1039/C8SC02535E	journal	January 2018
Thermodynamic and kinetic hydricity of transition metal hydrides Brereton, Kelsey R.; Smith, Nicholas E.; Hazari, Nilay Chemical Society Reviews, Vol. 49, Issue 22 https://doi.org/10.1039/D0CS00405G	journal	January 2020
Transition metal-catalyzed alkene isomerization as an enabling technology in tandem, sequential and domino processes Fiorito, Daniele; Scaringi, Simone; Mazet, Clément Chemical Society Reviews, Vol. 50, Issue 2 https://doi.org/10.1039/D0CS00449A	journal	January 2021
Mechanistic basis for tuning iridium hydride photochemistry from H ₂ evolution to hydride transfer hydrodechlorination Barrett, Seth M.; Stratakes, Bethany M.; Chambers, Matthew B. Chemical Science, Vol. 11, Issue 25 https://doi.org/10.1039/D0SC00422G	journal	January 2020
A framework for constructing linear free energy relationships to design molecular transition metal catalysts Lan, Zhenzhuo; Mallikarjun Sharada, Shaama Physical Chemistry Chemical Physics, Vol. 23, Issue 29 https://doi.org/10.1039/D1CP02278D	journal	January 2021
Recent developments in asymmetric hydroformylation Chakrabortty, Soumyadeep; Almasalma, Ahmad A.; de Vries, Johannes G. Catalysis Science & Technology, Vol. 11, Issue 16 https://doi.org/10.1039/D1CY00737H	journal	January 2021
C–H oxidation in fluorenyl benzoates does not proceed through a stepwise pathway: revisiting asynchronous proton-coupled electron transfer Coste, Scott C.; Brezny, Anna C.; Koronkiewicz, Brian Chemical Science, Vol. 12, Issue 39, p. 13127-13136 https://doi.org/10.1039/D1SC03344A	journal	September 2021
Synthesis of acridinesviacopper-catalyzed amination/annulation cascades between arylboronic acids and anthranils Li, Yuge; Xu, Liang; Wei, Yu Organic & Biomolecular Chemistry, Vol. 20, Issue 48 https://doi.org/10.1039/D2OB01705A	journal	January 2022
The multifarious world of transition metal hydrides McGrady, G. Sean; Guilera, Gemma Chemical Society Reviews, Vol. 32, Issue 6 https://doi.org/10.1039/b207999m	journal	January 2003
Mechanistic aspects of transition metal-catalyzed hydrogen transfer reactions Samec, Joseph S. M.; Bäckvall, Jan-E.; Andersson, Pher G. Chemical Society Reviews, Vol. 35, Issue 3 https://doi.org/10.1039/b515269k	journal	January 2006
The coordination chemistry of organo-hydride donors: new prospects for efficient multi-electron reduction McSkimming, Alex; Colbran, Stephen B. Chemical Society Reviews, Vol. 42, Issue 12 https://doi.org/10.1039/c3cs35466k	journal	January 2013
Solvent reorganization energy of electron-transfer reactions in polar solvents Matyushov, Dmitry V. The Journal of Chemical Physics, Vol. 120, Issue 16 https://doi.org/10.1063/1.1676122	journal	April 2004
Theory of Electron‐Transfer Reaction Rates of Solvated Electrons Marcus, R. A. The Journal of Chemical Physics, Vol. 43, Issue 10 https://doi.org/10.1063/1.1696504	journal	November 1965
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I Marcus, R. A. The Journal of Chemical Physics, Vol. 24, Issue 5 https://doi.org/10.1063/1.1742723	journal	May 1956
r ² SCAN-3c: A “Swiss army knife” composite electronic-structure method Grimme, Stefan; Hansen, Andreas; Ehlert, Sebastian The Journal of Chemical Physics, Vol. 154, Issue 6 https://doi.org/10.1063/5.0040021	journal	February 2021
Nuclear–electronic orbital methods: Foundations and prospects Hammes-Schiffer, Sharon The Journal of Chemical Physics, Vol. 155, Issue 3 https://doi.org/10.1063/5.0053576	journal	July 2021
Predicting organic hydrogen atom transfer rate constants using the Marcus cross relation Warren, J. J.; Mayer, J. M. Proceedings of the National Academy of Sciences, Vol. 107, Issue 12 https://doi.org/10.1073/pnas.0910347107	journal	March 2010
Beyond the classical thermodynamic contributions to hydrogen atom abstraction reactivity Bím, Daniel; Maldonado-Domínguez, Mauricio; Rulíšek, Lubomír Proceedings of the National Academy of Sciences, Vol. 115, Issue 44 https://doi.org/10.1073/pnas.1806399115	journal	September 2018
A new strategy to efficiently cleave and form C–H bonds using proton-coupled electron transfer Markle, Todd F.; Darcy, Julia W.; Mayer, James M. Science Advances, Vol. 4, Issue 7 https://doi.org/10.1126/sciadv.aat5776	journal	July 2018
π-π stacking interactions: Non-negligible forces for stabilizing porous supramolecular frameworks Deng, Ji-Hua; Luo, Jie; Mao, Yue-Lei Science Advances, Vol. 6, Issue 2 https://doi.org/10.1126/sciadv.aax9976	journal	January 2020
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
Chemical and Electrochemical Electron-Transfer Theory Marcus, R. A. Annual Review of Physical Chemistry, Vol. 15, Issue 1 https://doi.org/10.1146/annurev.pc.15.100164.001103	journal	October 1964

Similar Records

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

Journal Article · Wed Sep 21 00:00:00 EDT 2022 · Journal of the American Chemical Society · OSTI ID:1900392

Carbon Dioxide Insertion into Rhenium Hydrides as a Probe for the Impact of Solvent on Linear Free Energy Relationships between Thermodynamic and Kinetic Hydricity

Journal Article · Mon Oct 09 00:00:00 EDT 2023 · Organometallics · OSTI ID:2283306

Unexpected Hydricity of a Bis-Carbene Iridium Complex Provides Insight into Electronic Structure Impacts on Hydride Donor Ability

Journal Article · Wed Aug 20 00:00:00 EDT 2025 · Inorganic Chemistry · OSTI ID:2997743

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Hydride transfer
Thermodynamics
Transfer reactions
Transition states

Elucidation of Marcus Relationships for Hydride Transfer Reactions Involving Transition Metal Hydrides

Citation Formats

References (119)

Similar Records

Related Subjects