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 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.
- Authors:
-
[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:
- 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.
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
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.
@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 = {Wed Jan 24 00:00:00 EST 2018},
month = {Wed Jan 24 00:00:00 EST 2018}
}
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https://doi.org/10.1021/acscatal.7b03396
https://doi.org/10.1021/acscatal.7b03396
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Cited by: 135 works
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Figures / Tables:
Scheme 1: Modes of Metal−Hydride Bond Dissociation
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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)
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