Thermodynamic and kinetic hydricity of transition metal hydrides

Brereton, Kelsey R.; Smith, Nicholas E.; Hazari, Nilay; Miller, Alexander M.

doi:10.1039/d0cs00405g

Thermodynamic and kinetic hydricity of transition metal hydrides

Journal Article · Tue Aug 11 00:00:00 EDT 2020 · Chemical Society Reviews

DOI:https://doi.org/10.1039/d0cs00405g· OSTI ID:1851880

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

Pepperdine Univ., Malibu, CA (United States); OSTI
Yale Univ., New Haven, CT (United States)
Univ. of North Carolina, Chapel Hill, NC (United States)

The prevalence of transition metal-mediated hydride transfer reactions in chemical synthesis, catalysis, and biology has inspired the development of methods for characterizing the reactivity of transition metal hydride complexes. Thermodynamic hydricity represents the free energy required for heterolytic cleavage of the metal–hydride bond to release a free hydride ion, H^-, as determined through equilibrium measurements and thermochemical cycles. Kinetic hydricity represents the rate of hydride transfer from one species to another, as measured through kinetic analysis. This tutorial review describes the common methods for experimental and computational determination of thermodynamic and kinetic hydricity, including advice on best practices and precautions to help avoid pitfalls. The influence of solvation on hydricity is emphasized, including opportunities and challenges arising from comparisons across several different solvents. Connections between thermodynamic and kinetic hydricity are discussed, and opportunities for utilizing these connections to rationally improve catalytic processes involving hydride transfer are highlighted.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of North Carolina, Chapel Hill, NC (United States)

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

Grant/Contract Number:: SC0014255

OSTI ID:: 1851880

Alternate ID(s):: OSTI ID: 1714401

Journal Information:: Chemical Society Reviews, Journal Name: Chemical Society Reviews Journal Issue: 22 Vol. 49; ISSN 0306-0012

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Empirical Parameters of Solvent Polarity as Linear Free-Energy Relationships Reichardt, Christian Angewandte Chemie International Edition in English, Vol. 18, Issue 2 https://doi.org/10.1002/anie.197900981	journal	February 1979
Changing the Mechanism for CO ₂ Hydrogenation Using Solvent-Dependent Thermodynamics Burgess, Samantha A.; Appel, Aaron M.; Linehan, John C. Angewandte Chemie International Edition, Vol. 56, Issue 47 https://doi.org/10.1002/anie.201709319	journal	October 2017
Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential Cunningham, Drew W.; Barlow, Jeffrey M.; Velazquez, Reyna S. Angewandte Chemie International Edition, Vol. 59, Issue 11 https://doi.org/10.1002/anie.201913198	journal	February 2020
Catalytic Ionic Hydrogenations Bullock, R. Morris Chemistry - A European Journal, Vol. 10, Issue 10 https://doi.org/10.1002/chem.200305639	journal	May 2004
Synthesis and properties of [Ru(tpy)(4,4′-X2bpy)H]+ (tpy=2,2′:6′,2″-terpyridine, bpy=2,2′-bipyridine, X=H and MeO), and their reactions with CO2 Konno, Hideo; Kobayashi, Atsuo; Sakamoto, Kazuhiko Inorganica Chimica Acta, Vol. 299, Issue 2 https://doi.org/10.1016/S0020-1693(99)00488-0	journal	March 2000
Brønsted–Lowry Acid Strength of Metal Hydride and Dihydrogen Complexes Morris, Robert H. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.5b00695	journal	March 2016
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
Calculation of Reaction Free Energies in Solution: A Comparison of Current Approaches Besora, Maria; Vidossich, Pietro; Lledós, Agustí The Journal of Physical Chemistry A, Vol. 122, Issue 5 https://doi.org/10.1021/acs.jpca.7b11580	journal	January 2018
Aqueous Hydricity from Calculations of Reduction Potential and Acidity in Water Brereton, Kelsey R.; Bellows, Sarina M.; Fallah, Hengameh The Journal of Physical Chemistry B, Vol. 120, Issue 50 https://doi.org/10.1021/acs.jpcb.6b09864	journal	December 2016
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
Highly Selective Electrocatalytic CO ₂ Reduction by [Pt(dmpe) ₂ ] ²⁺ through Kinetic and Thermodynamic Control Ceballos, Bianca M.; Yang, Jenny Y. Organometallics, Vol. 39, Issue 9 https://doi.org/10.1021/acs.organomet.9b00720	journal	February 2020
Selectivity for HCO ₂ ^– over H ₂ in the Electrochemical Catalytic Reduction of CO ₂ by (POCOP)IrH ₂ Johnson, Samantha I.; Nielsen, Robert J.; Goddard, William A. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01755	journal	August 2016
Understanding the Relationship Between Kinetics and Thermodynamics in CO ₂ Hydrogenation Catalysis Jeletic, Matthew S.; Hulley, Elliott B.; Helm, Monte L. ACS Catalysis, Vol. 7, Issue 9 https://doi.org/10.1021/acscatal.7b01673	journal	August 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
Temperature-Dependent Transitions Between Normal and Inverse Isotope Effects Pertaining to the Interaction of H−H and C−H Bonds with Transition Metal Centers Parkin, Gerard Accounts of Chemical Research, Vol. 42, Issue 2 https://doi.org/10.1021/ar800156h	journal	February 2009
Development of Molecular Electrocatalysts for CO₂ Reduction and H₂ Production/Oxidation Rakowski Dubois, M.; Dubois, Daniel L. Accounts of Chemical Research, Vol. 42, Issue 12, p. 1974-1982 https://doi.org/10.1021/ar900110c	journal	December 2009
Kinetic Isotope Effects in the Study of Organometallic Reaction Mechanisms Gómez-Gallego, Mar; Sierra, Miguel A. Chemical Reviews, Vol. 111, Issue 8 https://doi.org/10.1021/cr100436k	journal	August 2011
Hydride Ion Transfer from Ruthenium(II) Complexes in Water: Kinetics and Mechanism Creutz, Carol; Chou, Mei H.; Hou, Hua Inorganic Chemistry, Vol. 49, Issue 21 https://doi.org/10.1021/ic101124q	journal	November 2010
Inter- and Intramolecular Experimental and Calculated Equilibrium Isotope Effects for (silox) ₂ ( ^t Bu ₃ SiND)TiR + RH (silox = ^t Bu ₃ SiO): Inferred Kinetic Isotope Effects for RH/D Addition to Transient (silox) ₂ TiNSi ^t Bu ₃ Slaughter, LeGrande M.; Wolczanski, Peter T.; Klinckman, Thomas R. Journal of the American Chemical Society, Vol. 122, Issue 33 https://doi.org/10.1021/ja000112q	journal	August 2000
Dissociative electron transfer. Homogeneous and heterogeneous reductive cleavage of the carbon-halogen bond in simple aliphatic halides Andrieux, Claude P.; Gallardo, Iluminada.; Savaent, Jean Michel. Journal of the American Chemical Society, Vol. 108, Issue 4 https://doi.org/10.1021/ja00264a013	journal	February 1986
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
Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO ₂ Reduction Catalyst Schmeier, Timothy J.; Dobereiner, Graham E.; Crabtree, Robert H. Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja2035514	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
A Cobalt-Based Catalyst for the Hydrogenation of CO ₂ under Ambient Conditions Jeletic, Matthew S.; Mock, Michael T.; Appel, Aaron M. Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja406601v	journal	July 2013
Hydricities of d ⁶ Metal Hydride Complexes in Water Creutz, Carol; Chou, Mei H. Journal of the American Chemical Society, Vol. 131, Issue 8 https://doi.org/10.1021/ja809724s	journal	March 2009
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
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
Relative Hydride, Proton, and Hydrogen Atom Transfer Abilities of [HM(diphosphine) ₂ ]PF ₆ Complexes (M = Pt, Ni) Berning, Douglas E.; Noll, Bruce C.; DuBois, Daniel L. Journal of the American Chemical Society, Vol. 121, Issue 49 https://doi.org/10.1021/ja991888y	journal	December 1999
Solvation Effects on Transition Metal Hydricity Tsay, Charlene; Livesay, Brooke N.; Ruelas, Samantha Journal of the American Chemical Society, Vol. 137, Issue 44 https://doi.org/10.1021/jacs.5b07777	journal	November 2015
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
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
Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 110, Issue 32 https://doi.org/10.1021/jp063552y	journal	August 2006
Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents Isse, Abdirisak A.; Gennaro, Armando The Journal of Physical Chemistry B, Vol. 114, Issue 23 https://doi.org/10.1021/jp100402x	journal	June 2010
Kinetic hydricity of transition-metal hydrides toward trityl cation Cheng, Tan-Yun; Bullock, R. Morris Organometallics, Vol. 14, Issue 9 https://doi.org/10.1021/om00009a001	journal	September 1995
Kinetics and mechanism of carbon dioxide insertion into a metal-hydride bond. A large solvent effect and an inverse kinetic isotope effect Sullivan, B. Patrick.; Meyer, Thomas J. Organometallics, Vol. 5, Issue 7 https://doi.org/10.1021/om00138a035	journal	July 1986
Hydride Transfer from (η ⁵ -C ₅ Me ₅ )(CO) ₂ MH (M = Fe, Ru, Os) to Trityl Cation: Different Products from Different Metals and the Kinetics of Hydride Transfer Cheng, Tan-Yun; Bullock, R. Morris Organometallics, Vol. 21, Issue 11 https://doi.org/10.1021/om020012o	journal	May 2002
Hydride Donor Abilities of Cationic Transition Metal Hydrides from DFT-PCM Calculations Kovács, Gábor; Pápai, Imre Organometallics, Vol. 25, Issue 4 https://doi.org/10.1021/om050726+	journal	January 2006
Ab Initio Calculations of Thermodynamic Hydricities of Transition-Metal Hydrides in Acetonitrile Qi, Xiu-Juan; Fu, Yao; Liu, Lei Organometallics, Vol. 26, Issue 17 https://doi.org/10.1021/om0702429	journal	August 2007
Comprehensive Thermodynamics of Nickel Hydride Bis(Diphosphine) Complexes: A Predictive Model through Computations Chen, Shentan; Rousseau, Roger; Raugei, Simone Organometallics, Vol. 30, Issue 22 https://doi.org/10.1021/om200645x	journal	November 2011
Predicting the reactivity of hydride donors in water: thermodynamic constants for hydrogen Connelly, Samantha J.; Wiedner, Eric S.; Appel, Aaron M. Dalton Transactions, Vol. 44, Issue 13 https://doi.org/10.1039/C4DT03841J	journal	January 2015
CO ₂ reduction or HCO ₂ ⁻ oxidation? Solvent-dependent thermochemistry of a nickel hydride complex Ceballos, Bianca M.; Tsay, Charlene; Yang, Jenny Y. Chemical Communications, Vol. 53, Issue 53 https://doi.org/10.1039/C7CC02511D	journal	January 2017
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
Influence of Lewis acid strength on hydride transfer to unsaturated substrates Kieffer, Ian A.; Treich, Nicholas R.; Fernandez, Jordan L. Dalton Transactions, Vol. 47, Issue 11 https://doi.org/10.1039/C7DT04929C	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
Structure–activity relationship study of half-sandwich metal complexes in aqueous transfer hydrogenation catalysis Ngo, Anh H.; Do, Loi H. Inorganic Chemistry Frontiers, Vol. 7, Issue 3 https://doi.org/10.1039/C9QI01310E	journal	January 2020
Calculation of thermodynamic hydricities and the design of hydride donors for CO2 reduction Muckerman, J. T.; Achord, P.; Creutz, C. Proceedings of the National Academy of Sciences, Vol. 109, Issue 39 https://doi.org/10.1073/pnas.1201026109	journal	July 2012
Directing the reactivity of metal hydrides for selective CO ₂ reduction Ceballos, Bianca M.; Yang, Jenny Y. Proceedings of the National Academy of Sciences, Vol. 115, Issue 50 https://doi.org/10.1073/pnas.1811396115	journal	November 2018

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Thermodynamic and kinetic hydricity of transition metal hydrides

Citation Formats

References (48)

Similar Records

Related Subjects