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Title: H 2 Oxidation Electrocatalysis Enabled by Metal‐to‐Metal Hydrogen Atom Transfer: A Homolytic Approach to a Heterolytic Reaction

Abstract

Abstract Oxidation of H 2 in a fuel cell converts the chemical energy of the H−H bond into electricity. Electrocatalytic oxidation of H 2 by molecular catalysts typically requires one metal to perform multiple chemical steps: bind H 2 , heterolytically cleave H 2 , and then undergo two oxidation and two deprotonation steps. The electrocatalytic oxidation of H 2 by a cooperative system using Cp*Cr(CO) 3 H and [Fe(diphosphine)(CO) 3 ] + has now been invetigated. A key step of the proposed mechanism is a rarely observed metal‐to‐metal hydrogen atom transfer from the Cr−H complex to the Fe, forming an Fe−H complex that is deprotonated and then oxidized electrochemically. This “division of chemical labor” features Cr interacting with H 2 to cleave the H−H bond, while Fe interfaces with the electrode. Neither metal is required to heterolytically cleave H 2 , so this system provides a very unusual example of a homolytic reaction being a key step in a molecular electrocatalytic process.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Center for Molecular Electrocatalysis Pacific Northwest National Laboratory Richland WA 99352 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1472167
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Name: Angewandte Chemie Journal Volume: 130 Journal Issue: 41; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Chambers, Geoffrey M., Wiedner, Eric S., and Bullock, R. Morris. H 2 Oxidation Electrocatalysis Enabled by Metal‐to‐Metal Hydrogen Atom Transfer: A Homolytic Approach to a Heterolytic Reaction. Germany: N. p., 2018. Web. doi:10.1002/ange.201807510.
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Chambers, Geoffrey M., Wiedner, Eric S., & Bullock, R. Morris. H 2 Oxidation Electrocatalysis Enabled by Metal‐to‐Metal Hydrogen Atom Transfer: A Homolytic Approach to a Heterolytic Reaction. Germany. https://doi.org/10.1002/ange.201807510
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Chambers, Geoffrey M., Wiedner, Eric S., and Bullock, R. Morris. Wed . "H 2 Oxidation Electrocatalysis Enabled by Metal‐to‐Metal Hydrogen Atom Transfer: A Homolytic Approach to a Heterolytic Reaction". Germany. https://doi.org/10.1002/ange.201807510.
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@article{osti_1472167,
title = {H 2 Oxidation Electrocatalysis Enabled by Metal‐to‐Metal Hydrogen Atom Transfer: A Homolytic Approach to a Heterolytic Reaction},
author = {Chambers, Geoffrey M. and Wiedner, Eric S. and Bullock, R. Morris},
abstractNote = {Abstract Oxidation of H 2 in a fuel cell converts the chemical energy of the H−H bond into electricity. Electrocatalytic oxidation of H 2 by molecular catalysts typically requires one metal to perform multiple chemical steps: bind H 2 , heterolytically cleave H 2 , and then undergo two oxidation and two deprotonation steps. The electrocatalytic oxidation of H 2 by a cooperative system using Cp*Cr(CO) 3 H and [Fe(diphosphine)(CO) 3 ] + has now been invetigated. A key step of the proposed mechanism is a rarely observed metal‐to‐metal hydrogen atom transfer from the Cr−H complex to the Fe, forming an Fe−H complex that is deprotonated and then oxidized electrochemically. This “division of chemical labor” features Cr interacting with H 2 to cleave the H−H bond, while Fe interfaces with the electrode. Neither metal is required to heterolytically cleave H 2 , so this system provides a very unusual example of a homolytic reaction being a key step in a molecular electrocatalytic process.},
doi = {10.1002/ange.201807510},
journal = {Angewandte Chemie},
number = 41,
volume = 130,
place = {Germany},
year = {Wed Sep 19 00:00:00 EDT 2018},
month = {Wed Sep 19 00:00:00 EDT 2018}
}
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https://doi.org/10.1002/ange.201807510
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