Concerted proton-coupled electron transfer from a metal-hydride complex

Marc Bourrez, Romain Steinmetz, Sascha Ott, Frederic Gloaguen, Leif Hammarström

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

Metal hydrides are key intermediates in the catalytic reduction of protons and CO2 as well as in the oxidation of H2. In these reactions, electrons and protons are transferred to or from separate acceptors or donors in bidirectional proton-coupled electron transfer (PCET) steps. The mechanistic interpretation of PCET reactions of metal hydrides has focused on the stepwise transfer of electrons and protons. A concerted transfer may, however, occur with a lower reaction barrier and therefore proceed at higher catalytic rates. Here we investigate the feasibility of such a reaction by studying the oxidation-deprotonation reactions of a tungsten hydride complex. The rate dependence on the driving force for both electron transfer and proton transfer - employing different combinations of oxidants and bases - was used to establish experimentally the concerted, bidirectional PCET of a metal-hydride species. Consideration of the findings presented here in future catalyst designs may lead to more-efficient catalysts.

Original languageEnglish
Pages (from-to)140-145
Number of pages6
JournalNature chemistry
Volume7
Issue number2
DOIs
Publication statusPublished - Jan 2015

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ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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