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

40 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 - 2015

Fingerprint

Hydrides
Protons
Metals
Electrons
Oxidation
Deprotonation
Catalysts
Tungsten
Proton transfer
Oxidants

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Concerted proton-coupled electron transfer from a metal-hydride complex. / Bourrez, Marc; Steinmetz, Romain; Ott, Sascha; Gloaguen, Frederic; Hammarström, Leif.

In: Nature Chemistry, Vol. 7, No. 2, 2015, p. 140-145.

Research output: Contribution to journalArticle

Bourrez, Marc ; Steinmetz, Romain ; Ott, Sascha ; Gloaguen, Frederic ; Hammarström, Leif. / Concerted proton-coupled electron transfer from a metal-hydride complex. In: Nature Chemistry. 2015 ; Vol. 7, No. 2. pp. 140-145.
@article{136b0a765b8745c18f3a7bf1f0d3d743,
title = "Concerted proton-coupled electron transfer from a metal-hydride complex",
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.",
author = "Marc Bourrez and Romain Steinmetz and Sascha Ott and Frederic Gloaguen and Leif Hammarstr{\"o}m",
year = "2015",
doi = "10.1038/nchem.2157",
language = "English",
volume = "7",
pages = "140--145",
journal = "Nature Chemistry",
issn = "1755-4330",
publisher = "Nature Publishing Group",
number = "2",

}

TY - JOUR

T1 - Concerted proton-coupled electron transfer from a metal-hydride complex

AU - Bourrez, Marc

AU - Steinmetz, Romain

AU - Ott, Sascha

AU - Gloaguen, Frederic

AU - Hammarström, Leif

PY - 2015

Y1 - 2015

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84923025895&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84923025895&partnerID=8YFLogxK

U2 - 10.1038/nchem.2157

DO - 10.1038/nchem.2157

M3 - Article

VL - 7

SP - 140

EP - 145

JO - Nature Chemistry

JF - Nature Chemistry

SN - 1755-4330

IS - 2

ER -