TY - JOUR
T1 - Homolytic X-H Bond Cleavage at a Gold(III) Hydroxide
T2 - Insights into One-Electron Events at Gold
AU - Engbers, Silène
AU - Leach, Isaac F.
AU - Havenith, Remco W.A.
AU - Klein, Johannes E.M.N.
N1 - Funding Information:
JEMNK and RWAH acknowledge access to computational facilities at the Peregrine high‐performance computing cluster (University of Groningen) and access to the national computing facilities provided by the Netherlands Organisation for Scientific Research (NWO project numbers 17664 and EINF‐2276), with support of the SURF Cooperative. JEMNK acknowledges funding from the Netherlands Organisation for Scientific Research (NWO START‐UP grant). IFL thanks the Dutch Ministry of Education, Culture, and Science (OCW) for funding his PhD scholarship.
Publisher Copyright:
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
PY - 2022/7
Y1 - 2022/7
N2 - C(sp3)-H and O−H bond breaking steps in the oxidation of 1,4-cyclohexadiene and phenol by a Au(III)-OH complex were studied computationally. The analysis reveals that for both types of bonds the initial X−H cleavage step proceeds via concerted proton coupled electron transfer (cPCET), reflecting electron transfer from the substrate directly to the Au(III) centre and proton transfer to the Au-bound oxygen. This mechanistic picture is distinct from the analogous formal Cu(III)-OH complexes studied by the Tolman group (J. Am. Chem. Soc. 2019, 141, 17236–17244), which proceed via hydrogen atom transfer (HAT) for C−H bonds and cPCET for O−H bonds. Hence, care should be taken when transferring concepts between Cu−OH and Au−OH species. Furthermore, the ability of Au−OH complexes to perform cPCET suggests further possibilities for one-electron chemistry at the Au centre, for which only limited examples exist.
AB - C(sp3)-H and O−H bond breaking steps in the oxidation of 1,4-cyclohexadiene and phenol by a Au(III)-OH complex were studied computationally. The analysis reveals that for both types of bonds the initial X−H cleavage step proceeds via concerted proton coupled electron transfer (cPCET), reflecting electron transfer from the substrate directly to the Au(III) centre and proton transfer to the Au-bound oxygen. This mechanistic picture is distinct from the analogous formal Cu(III)-OH complexes studied by the Tolman group (J. Am. Chem. Soc. 2019, 141, 17236–17244), which proceed via hydrogen atom transfer (HAT) for C−H bonds and cPCET for O−H bonds. Hence, care should be taken when transferring concepts between Cu−OH and Au−OH species. Furthermore, the ability of Au−OH complexes to perform cPCET suggests further possibilities for one-electron chemistry at the Au centre, for which only limited examples exist.
KW - computational chemistry
KW - gold
KW - oxidations
KW - proton coupled electron transfer
KW - reaction mechanisms
UR - http://www.scopus.com/inward/record.url?scp=85130995141&partnerID=8YFLogxK
U2 - 10.1002/chem.202200599
DO - 10.1002/chem.202200599
M3 - Article
AN - SCOPUS:85130995141
SN - 0947-6539
VL - 28
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 40
M1 - e202200599
ER -