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:1478363

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

Oxidation of H2 is used in the conversion of the chemical energy of the H-H bond into electricity. Electrocatalytic oxidation of H2 typically requires that one metal bind H2, heterolytically cleave the H2, and then undergo two oxidation and two deprotonation steps. We discovered that electrocatalytic oxidation of H2 is catalyzed by a cooperative system using Cp*Cr(CO)3H and [Fe(diphosphine)(CO)3]+. 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 a Fe-H bond that is deprotonated and then oxidized electrochemically. The “division of chemical labor” between Cr and Fe features a reaction of the Cr complex with H2, while the Fe complex reacts at the electrode. This cooperative catalysis system does not require that either metal heterolytically cleave H2, and thereby provides a very unusual example of a homolytic reaction being a key step in a molecular electrocatalytic process.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

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

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1478363

Report Number(s):: PNNL-SA-131196

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

Publisher:: Wiley

Country of Publication:: United States

Language:: English

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