Concerted proton-coupled electron transfer from a metal-hydride complex
2015 (English)In: Nature Chemistry, ISSN 1755-4330, E-ISSN 1755-4349, Vol. 7, no 2, 140-145 p.Article in journal (Refereed) Published
Metal hydrides are key intermediates in the catalytic reduction of protons and CO2 as well as in the oxidation of H-2. 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.
Place, publisher, year, edition, pages
2015. Vol. 7, no 2, 140-145 p.
IdentifiersURN: urn:nbn:se:uu:diva-246357DOI: 10.1038/NCHEM.2157ISI: 000348599600012OAI: oai:DiVA.org:uu-246357DiVA: diva2:793923