Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction

Waldie, Kate M.; Ostericher, Andrew L.; Reineke, Mark H.; Sasayama, Alissa F.; Kubiak, Clifford P.

doi:10.1021/acscatal.7b03396

Title: Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO ₂ Reduction

Abstract

The hydricity ΔG°_H- of a metal hydride is an important parameter for describing the reactivity of such complexes. Here, we compile a comprehensive data set consisting of 51 transition-metal hydride complexes [M-H]^(n-1)+ with known ΔG°_H- values in acetonitrile for which the one-electron reduction of the parent complex [M]ⁿ⁺ is reversible. Plotting the hydricity as a function of respective E_1/2(M^n+/(n-1)+) yields a robust linear correlation. While this correlation has been previously noted for limited data sets, our analysis demonstrates that this trend extends over a wide range of metal identities, ligand architectures, structural geometries, and overall charges of the metal hydride. This correlation is modeled using established thermochemical cycles relating the hydricity and homolytic bond free energy of the metal-hydride bond. The linear trend of the model enables the estimation of hydricity simply on the basis of the reduction potential of the parent complex and thus provides a guide for the rational design and tuning of metal hydride catalysts for small-molecule reduction, such as CO₂ to formic acid.

Authors:

^[1]; Ostericher, Andrew L. ^[1]; Reineke, Mark H. ^[1]; Sasayama, Alissa F. ^[1];

^[1]

Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, California 92093-0358, United States

Publication Date:: 2018-01-24

Research Org.:: Univ. of California, San Diego, CA (United States)

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

OSTI Identifier:: 1417924

Alternate Identifier(s):: OSTI ID: 1508329

Grant/Contract Number:: SC0004993

Resource Type:: Published Article

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Name: ACS Catalysis Journal Volume: 8 Journal Issue: 2; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon dioxide; catalyst design; CO2 hydrogenation; CO2 reduction; formic acid; hydricity; transition-metal hydride

Citation Formats


                    Waldie, Kate M., Ostericher, Andrew L., Reineke, Mark H., Sasayama, Alissa F., and Kubiak, Clifford P.. Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction.  United States: N. p., 2018. 
Web.  doi:10.1021/acscatal.7b03396.

Copy to clipboard


                    Waldie, Kate M., Ostericher, Andrew L., Reineke, Mark H., Sasayama, Alissa F., & Kubiak, Clifford P.. Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction.  United States.  https://doi.org/10.1021/acscatal.7b03396

Copy to clipboard


                    Waldie, Kate M., Ostericher, Andrew L., Reineke, Mark H., Sasayama, Alissa F., and Kubiak, Clifford P.. Wed .  
"Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction".  United States.  https://doi.org/10.1021/acscatal.7b03396.

Copy to clipboard


                    
@article{osti_1417924,

  title        = {Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction},

  author       = {Waldie, Kate M. and Ostericher, Andrew L. and Reineke, Mark H. and Sasayama, Alissa F. and Kubiak, Clifford P.},

  abstractNote = {The hydricity ΔG°H- of a metal hydride is an important parameter for describing the reactivity of such complexes. Here, we compile a comprehensive data set consisting of 51 transition-metal hydride complexes [M-H](n-1)+ with known ΔG°H- values in acetonitrile for which the one-electron reduction of the parent complex [M]n+ is reversible. Plotting the hydricity as a function of respective E1/2(Mn+/(n-1)+) yields a robust linear correlation. While this correlation has been previously noted for limited data sets, our analysis demonstrates that this trend extends over a wide range of metal identities, ligand architectures, structural geometries, and overall charges of the metal hydride. This correlation is modeled using established thermochemical cycles relating the hydricity and homolytic bond free energy of the metal-hydride bond. The linear trend of the model enables the estimation of hydricity simply on the basis of the reduction potential of the parent complex and thus provides a guide for the rational design and tuning of metal hydride catalysts for small-molecule reduction, such as CO2 to formic acid.},

  doi          = {10.1021/acscatal.7b03396},

  journal      = {ACS Catalysis},

  number       = 2,

  volume       = 8,

  place        = {United States},

  year         = {2018},

  month        = {1}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1021/acscatal.7b03396

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 135 works

Citation information provided by
Web of Science

Figures / Tables:

Scheme 1: Modes of Metal−Hydride Bond Dissociation

All figures and tables (19 total)

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

Role of Ligand in the Selective Production of Hydrogen from Formic Acid Catalysed by the Mononuclear Cationic Zinc Complexes [(L)Zn(H)] ⁺ (L=tpy, phen, and bpy)
journal, July 2019

Piacentino, Elettra L.; Parker, Kevin; Gilbert, Thomas M.
Chemistry – A European Journal, Vol. 25, Issue 42
DOI: 10.1002/chem.201901360

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity
journal, August 2019

Kruppa, Sebastian V.; Groß, Cedric; Gui, Xin
Chemistry – A European Journal
DOI: 10.1002/chem.201901981

A look at periodic trends in d-block molecular electrocatalysts for CO ₂ reduction
journal, January 2019

Jiang, Changcheng; Nichols, Asa W.; Machan, Charles W.
Dalton Transactions, Vol. 48, Issue 26
DOI: 10.1039/c9dt00491b

Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts
journal, January 2019

Ramakrishnan, Srinivasan; Moretti, Ross A.; Chidsey, Christopher E. D.
Chemical Science, Vol. 10, Issue 32
DOI: 10.1039/c9sc01766f

Electrocatalytic H 2 Evolution by the Co‐Mabiq Complex Requires Tempering of the Redox‐Active Ligand
journal, June 2019

Tok, G. Ceren; Freiberg, Anna T. S.; Gasteiger, Hubert A.
ChemCatChem, Vol. 11, Issue 16
DOI: 10.1002/cctc.201900953

Electrocatalytic H 2 Evolution by the Co‐Mabiq Complex Requires Tempering of the Redox‐Active Ligand
journal, June 2019

Tok, G. Ceren; Freiberg, Anna T. S.; Gasteiger, Hubert A.
ChemCatChem, Vol. 11, Issue 16
DOI: 10.1002/cctc.201900953

Role of Ligand in the Selective Production of Hydrogen from Formic Acid Catalysed by the Mononuclear Cationic Zinc Complexes [(L)Zn(H)] ⁺ (L=tpy, phen, and bpy)
journal, July 2019

Piacentino, Elettra L.; Parker, Kevin; Gilbert, Thomas M.
Chemistry – A European Journal, Vol. 25, Issue 42
DOI: 10.1002/chem.201901360

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity
journal, August 2019

Kruppa, Sebastian V.; Groß, Cedric; Gui, Xin
Chemistry – A European Journal
DOI: 10.1002/chem.201901981

A look at periodic trends in d-block molecular electrocatalysts for CO ₂ reduction
journal, January 2019

Jiang, Changcheng; Nichols, Asa W.; Machan, Charles W.
Dalton Transactions, Vol. 48, Issue 26
DOI: 10.1039/c9dt00491b

Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts
journal, January 2019

Ramakrishnan, Srinivasan; Moretti, Ross A.; Chidsey, Christopher E. D.
Chemical Science, Vol. 10, Issue 32
DOI: 10.1039/c9sc01766f

Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential
journal, March 2020

Cunningham, Drew W.; Barlow, Jeffrey M.; Velazquez, Reyna S.
Angewandte Chemie, Vol. 132, Issue 11
DOI: 10.1002/ange.201913198

Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential
journal, February 2020

Cunningham, Drew W.; Barlow, Jeffrey M.; Velazquez, Reyna S.
Angewandte Chemie International Edition, Vol. 59, Issue 11
DOI: 10.1002/anie.201913198

Making a Splash in Homogeneous CO ₂ Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms
journal, July 2018

Wiedner, Eric S.; Linehan, John C.
Chemistry – A European Journal, Vol. 24, Issue 64
DOI: 10.1002/chem.201801759

Hydride Pinning Pathway in the Hydrogenation of CO ₂ to Formic Acid on Dimeric Tin Dioxide
journal, February 2019

Sarma, Plaban Jyoti; Baruah, Satyajit Dey; Logsdail, Andrew
ChemPhysChem, Vol. 20, Issue 5
DOI: 10.1002/cphc.201801194

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO ₂
journal, September 2019

Chen, Jiawei; McGraw, Michael; Chen, Eugene Y. ‐X.
ChemSusChem, Vol. 12, Issue 20
DOI: 10.1002/cssc.201901764

Unambiguous hydrogenation of CO ₂ by coinage-metal hydride anions: an intuitive idea based on in silico experiments
journal, January 2019

Habib, Md; Sarkar, Ritabrata; Biswas, Santu
Physical Chemistry Chemical Physics, Vol. 21, Issue 14
DOI: 10.1039/c9cp00133f

Thermodynamic targeting of electrocatalytic CO ₂ reduction: advantages, limitations, and insights for catalyst design
journal, January 2019

Ostericher, Andrew L.; Porter, Tyler M.; Reineke, Mark H.
Dalton Transactions, Vol. 48, Issue 42
DOI: 10.1039/c9dt03255j

Bulk gold catalyzes hydride transfer in the Cannizzaro and related reactions
journal, January 2019

Fecteau, Kristopher M.; Gould, Ian R.; Williams, Lynda B.
New Journal of Chemistry, Vol. 43, Issue 48
DOI: 10.1039/c9nj04029c

[Re(η ⁶ -arene) ₂ ] ⁺ as a highly stable ferrocene-like scaffold for ligands and complexes
journal, January 2020

Hernández-Valdés, Daniel; Avignon, Frédéric; Müller, Peter
Dalton Transactions, Vol. 49, Issue 16
DOI: 10.1039/d0dt00731e

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Thermodynamic Hydricities of Biomimetic Organic Hydride Donors

Journal Article Ilic, Stefan ; Kadel, Usha Pandey ; Basdogan, Yasemin ; ... - Journal of the American Chemical Society

Here, thermodynamic hydricities (ΔG_H^–) in acetonitrile and dimethyl sulfoxide have been calculated and experimentally measured for several metal-free hydride donors: NADH analogs (BNAH, CN-BNAH, Me-MNAH, HEH), methylene tetrahydromethanopterin analogs (BIMH, CAFH), acridine derivatives (Ph-AcrH, Me₂N-AcrH, T-AcrH, 4OH, 2OH, 3NH), and a triarylmethane derivative (6OH). The calculated hydricity values, obtained using density functional theory, showed a reasonably good match (within 3 kcal/mol) with the experimental values, obtained using “potential pK_a” and “hydride-transfer” methods. The hydride donor abilities of model compounds were in the 48.7–85.8 kcal/mol (acetonitrile) and 46.9–84.1 kcal/mol (DMSO) range, making them comparable to previously studied first-row transition metal hydridemore »« less
Cited by 44
https://doi.org/10.1021/jacs.7b13526

Full Text Available
Thermodynamic and kinetic hydricities of metal-free hydrides

Journal Article Ilic, Stefan ; Alherz, Abdulaziz ; Musgrave, Charles B. ; ... - Chemical Society Reviews

Metal-free hydrides are of increasing research interest due to their roles in recent scientific advances in catalysis, such as hydrogen activation with frustrated Lewis pairs and electrocatalytic CO₂ reduction with pyridinium and other aromatic cations. The structural design of hydrides for specific applications necessitates the correct description of their thermodynamic and kinetic prowess using reliable parameters – thermodynamic hydricity (ΔG_H^–) and nucleophilicity (N). This review summarizes reported experimental and calculated hydricity values for more than 200 metal-free hydride donors, including carbon-, boron-, nitrogen- and silicon-based hydrides. We describe different experimental and computational methods used to obtain these thermodynamic and kineticmore »« less
Cited by 69
https://doi.org/10.1039/C7CS00171A

Full Text Available
Thermodynamic Hydricity of Transition Metal Hydrides

Journal Article Wiedner, Eric S. ; Chambers, Matthew B. ; Pitman, Catherine L. ; ... - Chemical Reviews

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 themore »« less
Cited by 294
https://doi.org/10.1021/acs.chemrev.6b00168
Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

Journal Article Espinosa, Matthew R. ; Ertem, Mehmed Z. ; Barakat, Mariam ; ... - Journal of the American Chemical Society

The kinetics of hydride transfer from Re(^Rbpy)(CO)₃H (bpy = 4,4'-R-2,2'-bipyridine; R = OMe, ^tBu, Me, H, Br, COOMe, CF₃) to CO₂ and seven different cationic N-heterocycles were determined. Additionally, the thermodynamic hydricities of complexes of the type Re(^Rbpy)(CO)₃H were established primarily using computational methods. Linear free-energy relationships (LFERs) derived by correlating thermodynamic and kinetic hydricities indicate that, in general, the rate of hydride transfer increases as the thermodynamic driving force for the reaction increases. Kinetic isotope effects range from inverse for hydride transfer reactions with a small driving force to normal for reactions with a large driving force. Hammett analysismore »« less
https://doi.org/10.1021/jacs.2c07192

Full Text Available
Distinct Mechanisms and Hydricities of Cp*Ir-Based CO₂ Hydrogenation Catalysts in Basic Water

Journal Article Nijamudheen, A. ; Kanega, Ryoichi ; Onishi, Naoya ; ... - ACS Catalysis

Transition metal-catalyzed reversible hydrogenation of CO₂ to formate in aqueous solutions under ambient conditions is an attractive environmentally friendly strategy for the storage and transportation of H₂ in a liquid chemical form. Here, mechanistic details for the CO₂ hydrogenation by a series of pentamethylcyclopentadienyl iridium(III) (Cp*Ir) complexes with picolinamidate ligands are investigated through density functional theory and kinetic isotope effects (KIEs) calculations. Additionally, adopting a speciation approach at a pH of 8.2, CO₂ hydrogenation mechanisms of 37 distinct protonation states and conformers of Cp*Ir type complexes are investigated. This imposes a challenging test for the computational modeling in terms ofmore »« less
https://doi.org/10.1021/acscatal.0c04772

Full Text Available

Similar Records

Title: Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction

Abstract

Citation Formats

Figures / Tables:

Role of Ligand in the Selective Production of Hydrogen from Formic Acid Catalysed by the Mononuclear Cationic Zinc Complexes [(L)Zn(H)] + (L=tpy, phen, and bpy) journal, July 2019

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity journal, August 2019

A look at periodic trends in d-block molecular electrocatalysts for CO 2 reduction journal, January 2019

Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts journal, January 2019

Electrocatalytic H 2 Evolution by the Co‐Mabiq Complex Requires Tempering of the Redox‐Active Ligand journal, June 2019

Electrocatalytic H 2 Evolution by the Co‐Mabiq Complex Requires Tempering of the Redox‐Active Ligand journal, June 2019

Role of Ligand in the Selective Production of Hydrogen from Formic Acid Catalysed by the Mononuclear Cationic Zinc Complexes [(L)Zn(H)] + (L=tpy, phen, and bpy) journal, July 2019

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity journal, August 2019

A look at periodic trends in d-block molecular electrocatalysts for CO 2 reduction journal, January 2019

Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts journal, January 2019

Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential journal, March 2020

Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential journal, February 2020

Making a Splash in Homogeneous CO 2 Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms journal, July 2018

Hydride Pinning Pathway in the Hydrogenation of CO 2 to Formic Acid on Dimeric Tin Dioxide journal, February 2019

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO 2 journal, September 2019

Unambiguous hydrogenation of CO 2 by coinage-metal hydride anions: an intuitive idea based on in silico experiments journal, January 2019

Thermodynamic targeting of electrocatalytic CO 2 reduction: advantages, limitations, and insights for catalyst design journal, January 2019

Bulk gold catalyzes hydride transfer in the Cannizzaro and related reactions journal, January 2019

[Re(η 6 -arene) 2 ] + as a highly stable ferrocene-like scaffold for ligands and complexes journal, January 2020

Title: Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO ₂ Reduction

Role of Ligand in the Selective Production of Hydrogen from Formic Acid Catalysed by the Mononuclear Cationic Zinc Complexes [(L)Zn(H)] ⁺ (L=tpy, phen, and bpy)
journal, July 2019

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity
journal, August 2019

A look at periodic trends in d-block molecular electrocatalysts for CO ₂ reduction
journal, January 2019

Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts
journal, January 2019

Electrocatalytic H 2 Evolution by the Co‐Mabiq Complex Requires Tempering of the Redox‐Active Ligand
journal, June 2019

Electrocatalytic H 2 Evolution by the Co‐Mabiq Complex Requires Tempering of the Redox‐Active Ligand
journal, June 2019

Role of Ligand in the Selective Production of Hydrogen from Formic Acid Catalysed by the Mononuclear Cationic Zinc Complexes [(L)Zn(H)] ⁺ (L=tpy, phen, and bpy)
journal, July 2019

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity
journal, August 2019

A look at periodic trends in d-block molecular electrocatalysts for CO ₂ reduction
journal, January 2019

Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts
journal, January 2019

Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential
journal, March 2020

Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential
journal, February 2020

Making a Splash in Homogeneous CO ₂ Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms
journal, July 2018

Hydride Pinning Pathway in the Hydrogenation of CO ₂ to Formic Acid on Dimeric Tin Dioxide
journal, February 2019

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO ₂
journal, September 2019

Unambiguous hydrogenation of CO ₂ by coinage-metal hydride anions: an intuitive idea based on in silico experiments
journal, January 2019

Thermodynamic targeting of electrocatalytic CO ₂ reduction: advantages, limitations, and insights for catalyst design
journal, January 2019

Bulk gold catalyzes hydride transfer in the Cannizzaro and related reactions
journal, January 2019

[Re(η ⁶ -arene) ₂ ] ⁺ as a highly stable ferrocene-like scaffold for ligands and complexes
journal, January 2020