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

Silène Engbers, Isaac F. Leach, Remco W.A. Havenith, Johannes E.M.N. Klein*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

6 Citations (Scopus)
65 Downloads (Pure)

Abstract

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.

Original languageEnglish
Article numbere202200599
Number of pages6
JournalChemistry - A European Journal
Volume28
Issue number40
Early online date4-May-2022
DOIs
Publication statusPublished - Jul-2022

Keywords

  • computational chemistry
  • gold
  • oxidations
  • proton coupled electron transfer
  • reaction mechanisms

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