Affiliation:
1. Molecular Inorganic Chemistry Stratingh Institute for Chemistry Faculty of Science and Engineering University of Groningen Nijenborgh 4 9747 AG Groningen The Netherlands
Abstract
AbstractWe report the preparation and characterization of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) and study its reactivity towards weak X−H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton‐coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au−Au σ‐bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)−H bond cleavage. We thus describe the oxidation event as a valence tautomerism‐induced PCET where the basicity of one reduced Au−OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical‐type reactivity by a closed shell AuII complex.
Funder
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Cited by
4 articles.
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