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Title: Thermodynamic Hydricity of Transition Metal Hydrides

Journal Article · · Chemical Reviews
 [1];  [2];  [2];  [1];  [2];  [1]
  1. Pacific Northwest National Laboratory, Richland, Washington 99352, United States
  2. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States

Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds can enable the prediction of chemical reactivity, such as for the bond-forming and bond-breaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M–H bond to generate a hydride ion (H–). Three primary methods have been developed for hydricity determination: the “reference hydride” method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the “H2 heterolysis” method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the “potential–pKa” method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen. E.S.W. and A.M.A. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. R.M.B. was supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy. M.B.C. and A.J.M.M. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences (DE-SC0014255). C.L.P. was supported by the National Science Foundation Center for Enabling New Technologies through Catalysis (CHE-1205189) and the Royster Society of Fellows (C.L.P.).

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0014255; CHE-1205189; AC05-76RL01830
OSTI ID:
1280195
Alternate ID(s):
OSTI ID: 1313998; OSTI ID: 1773427
Report Number(s):
PNNL-SA-116484
Journal Information:
Chemical Reviews, Journal Name: Chemical Reviews Vol. 116 Journal Issue: 15; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 327 works
Citation information provided by
Web of Science

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  • Ciancanelli, Rebecca; Noll, Bruce C.; DuBois, Daniel L.
  • Journal of the American Chemical Society, Vol. 124, Issue 12, p. 2984-2992 https://doi.org/10.1021/ja0122804
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Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD + journal August 2012
Metal−Ligand Bifunctional Catalysis:  A Nonclassical Mechanism for Asymmetric Hydrogen Transfer between Alcohols and Carbonyl Compounds journal November 2001
The coordination chemistry of organo-hydride donors: new prospects for efficient multi-electron reduction journal January 2013
Thermodynamic Scales for Sulfur Atom Transfer and Oxo-for-Sulfido Exchange Reactions journal November 2006
CO 2 Hydrogenation to Formate and Methanol as an Alternative to Photo- and Electrochemical CO 2 Reduction journal August 2015
Hydride transfer and dihydrogen elimination from osmium and ruthenium metalloporphyrin hydrides: model processes for hydrogenase enzymes and the hydrogen electrode reaction journal July 1992
Catalysis of the electrochemical reduction of carbon dioxide journal January 2013
The Remarkable Reactivity of High Oxidation State Ruthenium and Osmium Polypyridyl Complexes journal December 2003
Acidities of water and simple alcohols in dimethyl sulfoxide solution journal August 1980
[Ni(Et 2 PCH 2 NMeCH 2 PEt 2 ) 2 ] 2+ as a Functional Model for Hydrogenases journal January 2003
Synthesis of transition metal formyl compounds by nucleophilic attack of hydride on coordinated carbon monoxide journal August 1976
Regioselective Reduction of NAD+ Models with [Cp*Rh(bpy)H]+: Structure-Activity Relationships and Mechanistic Aspects in the Formation of the 1,4-NADH Derivatives journal May 1999
Cooperative Catalysis with First-Row Late Transition Metals journal September 2011
Analytical study of a series of substituted (2,2'-bipyridyl)(pentamethylcyclopentadienyl)rhodium and -iridium complexes with regard to their effectiveness as redox catalysts for the indirect electrochemical and chemical reduction of NAD(P)+ journal May 1991
Acid-base equilibriums in dipolar aprotic solvents journal November 1974
L’incarnation d’une idée book January 1992
Hydrogen Generation from Weak Acids: Electrochemical and Computational Studies in the [(η 5 -C 5 H 5 )Fe(CO) 2 ] 2 System journal September 2008
Efficient Catalytic Interconversion between NADH and NAD + Accompanied by Generation and Consumption of Hydrogen with a Water-Soluble Iridium Complex at Ambient Pressure and Temperature journal December 2011
Hydricity of an Fe–H Species and Catalytic CO 2 Hydrogenation journal December 2014
Reactions of tris- and bis(2,2'-bipyridine)rhodium(II) complexes in aqueous solution journal March 1983
Ammonia-Borane and Related Compounds as Dihydrogen Sources journal July 2010
Hydride Reduction of NAD(P) + Model Compounds with a Ru(II)–Hydrido Complex journal November 2015
Visible light photocatalytic reduction of aldehydes by Rh( iii )–H: a detailed mechanistic study journal January 2015
Thermodynamic Diagnosis of the Properties and Mechanism of Dihydropyridine-Type Compounds as Hydride Source in Acetonitrile with “Molecule ID Card” journal February 2010
Structure sensitivity of the Marcus .lambda. for hydride transfer between NAD+ analogs journal January 1988
Recommendations on reporting electrode potentials in nonaqueous solvents (Recommendations 1983) journal January 1984
Evaluation of Homogeneous Electrocatalysts by Cyclic Voltammetry journal September 2014
Oxidation of Toluene by [(phen) 2 Mn(μ-O) 2 Mn(phen) 2 ] 4+ via Initial Hydride Abstraction journal December 1999
Development of Molecular Electrocatalysts for Energy Storage journal February 2014
Solution homolytic bond dissociation energies of organotransition-metal hydrides journal August 1989
A potentiometric study of acid–base equilibria of substituted pyridines in acetonitrile journal February 1999
Photoswitchable Hydride Transfer from Iridium to 1-Methylnicotinamide Rationalized by Thermochemical Cycles journal October 2014
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications journal December 2010
Towards a Comprehensive Hydride Donor Ability Scale journal November 2012
Scales of Nucleophilicity and Electrophilicity: A System for Ordering Polar Organic and Organometallic Reactions journal May 1994
Substituent Effects on Cobalt Diglyoxime Catalysts for Hydrogen Evolution journal November 2011
Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes journal May 2016
Properties of Bases in Acetonitrile as Solvent. IV. Proton Acceptor Power and Homoconjugation of Mono- and Diamines journal November 1965
Calculation of thermodynamic hydricities and the design of hydride donors for CO2 reduction journal July 2012
Making C–H bonds with CO 2 : production of formate by molecular electrocatalysts journal January 2016
Heterolytic dihydrogen activation by B(C6F5)3 and carbonyl compounds journal January 2012
Determining the Overpotential for a Molecular Electrocatalyst journal December 2013
An Iron Electrocatalyst for Selective Reduction of CO 2 to Formate in Water: Including Thermochemical Insights journal November 2015
Kinetic hydricity of transition-metal hydrides toward trityl cation journal September 1995
Oxidation of Benzyl Alcohol by a Dioxo Complex of Ruthenium(VI) journal May 1999
Enzymes in organic synthesis: oxidoreductions journal January 1995
Metal-Hydrogen Bond Cleavage Reactions of Transition Metal Hydrides: Hydrogen Atom, Hydride, and Proton Transfer Reactions journal May 1991
Boryl–Metal Bonds Facilitate Cobalt/Nickel-Catalyzed Olefin Hydrogenation journal September 2014
Asymmetric Transfer Hydrogenation Catalyzed by Chiral Ruthenium Complexes journal February 1997
Basicity of Phosphanes and Diphosphanes in Acetonitrile journal February 2012
Boryl-Mediated Reversible H 2 Activation at Cobalt: Catalytic Hydrogenation, Dehydrogenation, and Transfer Hydrogenation journal October 2013
Photochemical and Radiolytic Production of an Organic Hydride Donor with a RuII Complex Containing an NAD+ Model Ligand journal May 2007
Facile Heterolytic Cleavage of Dihydrogen by Phosphines and Boranes journal February 2007
TMC Literature Highlights—30: C2 compounds directly from synthesis gas via organometallic catalysts journal October 1992
Isomerization of Allylbenzenes journal May 2015
Estimates of hydride ion stability in condensed systems: energy of formation and solvation in aqueous and polar-organic solvents journal January 2001
Oxidation-Reduction Potentials of the Diphosphopyridine Nucleotide System journal April 1955
Hydride transfer reactions of transition metal hydrides in the preparation of [Cp(CO)3W(η1-aldehyde)]+OTf− and [Cp(CO)3W(η1-ketone)]+OTf− complexes journal June 1997
Establishing the Hydride Donor Abilities of Main Group Hydrides journal May 2015
Multiple Pathways for Benzyl Alcohol Oxidation by Ru V ═O 3+ and Ru IV ═O 2+ journal February 2011
σ-Acceptor, Z-type ligands for transition metals journal January 2011
Carbon monoxide and carbon dioxide fixation: relevant C1 and C2 ligand reactions emphasizing (.eta.5-C5H5)Fe-containing complexes journal November 1988
Thermodynamic Studies and Hydride Transfer Reactions from a Rhodium Complex to BX 3 Compounds journal October 2009
Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation journal December 2009
Tailoring Electrocatalysts for Selective CO 2 or H + Reduction: Iron Carbonyl Clusters as a Case Study journal November 2015
Free Energy Landscapes for S−H Bonds in Cp* 2 Mo 2 S 4 Complexes journal April 2009
Electrocatalytic and homogeneous approaches to conversion of CO 2 to liquid fuels journal January 2009
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 journal March 2000
Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents journal February 1993
Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts journal July 2007
Pentakis(trifluoromethyl)phenyl, a Sterically Crowded and Electron-withdrawing Group:  Synthesis and Acidity of Pentakis(trifluoromethyl)benzene, -toluene, -phenol, and -aniline journal April 2008
Group 10 and 11 Metal Boratranes (Ni, Pd, Pt, CuCl, AgCl, AuCl, and Au + ) Derived from a Triphosphine−Borane journal December 2008
Relative reactivities of anionic transition metal hydrides. Reduction of alkyl halides journal April 1984
Thermodynamics of the Metal–Hydrogen Bonds in (η 5 -C 5 H 5 )M(CO) 2 H (M = Fe, Ru, Os) journal June 2011
Relative rates of hydrogen atom (H.cntdot.) transfer from transition-metal hydrides to trityl radicals journal June 1991
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation journal June 2013
Fuel from Water: The Photochemical Generation of Hydrogen from Water journal June 2014
Ab Initio Calculations of p K a Values of Transition-Metal Hydrides in Acetonitrile journal December 2006
A Thermodynamic Analysis of Rhenium(I)–Formyl C–H Bond Formation via Base-Assisted Heterolytic H 2 Cleavage in the Secondary Coordination Sphere journal September 2013
Acid−Base Equilibria in Nonpolar Media. 1. A Spectrophotometric Method for Acidity Measurements in Heptane journal November 1997
Water-Soluble Phenanthroline Complexes of Rhodium, Iridium and Ruthenium for the Regeneration of NADH in the Enzymatic Reduction of Ketones journal October 2007