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

Chambers, Geoffrey M.; Wiedner, Eric S.; Bullock, R. Morris

doi:10.1002/anie.201807510

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

Journal Article · Wed Sep 19 00:00:00 EDT 2018 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201807510· OSTI ID:1472165

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Center for Molecular Electrocatalysis Pacific Northwest National Laboratory Richland WA 99352 USA

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.

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Sponsoring Organization:: USDOE

OSTI ID:: 1472165

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Vol. 57 Journal Issue: 41; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 9 works

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

Journal Article · Wed Sep 19 00:00:00 EDT 2018 · Angewandte Chemie · OSTI ID:1472165

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

Journal Article · Wed Sep 19 00:00:00 EDT 2018 · Angewandte Chemie (International Edition) · OSTI ID:1472165

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