Homolytic X-H Bond Cleavage at a Gold(III) Hydroxide: Insights into One-Electron Events at Gold

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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.

Originele taal-2English
Artikelnummere202200599
Aantal pagina's6
TijdschriftChemistry - A European Journal
Volume28
Nummer van het tijdschrift40
Vroegere onlinedatum4-mei-2022
DOI's
StatusPublished - jul-2022

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