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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 CO 2 to formic acid.

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of California, San Diego, CA (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) (SC-22)
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 Volume: 8; Journal Issue: 2; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
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 CO2 Reduction. United States: N. p., 2017. 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 CO2 Reduction. United States. doi:10.1021/acscatal.7b03396.
Waldie, Kate M., Ostericher, Andrew L., Reineke, Mark H., Sasayama, Alissa F., and Kubiak, Clifford P. Fri . "Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO2 Reduction". United States. doi:10.1021/acscatal.7b03396.
@article{osti_1417924,
title = {Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO2 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 = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acscatal.7b03396

Citation Metrics:
Cited by: 23 works
Citation information provided by
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