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Homolytic X‐H Bond Cleavage at a Gold(III) Hydroxide: Insights into One‐Electron Events at Gold
Author(s) -
Engbers Silène,
Leach Isaac F.,
Havenith Remco W. A.,
Klein Johannes E. M. N.
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200599
Subject(s) - chemistry , electron transfer , bond cleavage , hydroxide , crystallography , proton , homolysis , cleavage (geology) , hydrogen bond , hydrogen atom , photochemistry , molecule , inorganic chemistry , catalysis , group (periodic table) , radical , organic chemistry , materials science , physics , quantum mechanics , fracture (geology) , composite material
C(sp 3 )‐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.