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Accelerating proton-coupled electron transfer of metal hydrides in catalyst model reactions
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.ORCID iD: 0000-0001-5403-9902
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
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2018 (English)In: Nature Chemistry, ISSN 1755-4330, E-ISSN 1755-4349, Vol. 10, no 8, p. 881-887Article in journal (Refereed) Published
Abstract [en]

Metal hydrides are key intermediates in catalytic proton reduction and dihydrogen oxidation. There is currently much interest in appending proton relays near the metal centre to accelerate catalysis by proton-coupled electron transfer (PCET). However, the elementary PCET steps and the role of the proton relays are still poorly understood, and direct kinetic studies of these processes are scarce. Here, we report a series of tungsten hydride complexes as proxy catalysts, with covalently attached pyridyl groups as proton acceptors. The rate of their PCET reaction with external oxidants is increased by several orders of magnitude compared to that of the analogous systems with external pyridine on account of facilitated proton transfer. Moreover, the mechanism of the PCET reaction is altered by the appended bases. A unique feature is that the reaction can be tuned to follow three distinct PCET mechanisms-electron-first, proton-first or a concerted reaction-with very different sensitivities to oxidant and base strength. Such knowledge is crucial for rational improvements of solar fuel catalysts.

Place, publisher, year, edition, pages
2018. Vol. 10, no 8, p. 881-887
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Physical Chemistry
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URN: urn:nbn:se:uu:diva-357209DOI: 10.1038/s41557-018-0076-xISI: 000439420400015PubMedID: 30013192OAI: oai:DiVA.org:uu-357209DiVA, id: diva2:1238500
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Swedish Research Council, 2016-04271Knut and Alice Wallenberg Foundation, 2011.0067Available from: 2018-08-13 Created: 2018-08-13 Last updated: 2019-01-04Bibliographically approved

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