Four-Electron Oxidation of Phenols to p-Benzoquinone Imines by a (Salen)ruthenium(VI) Nitrido Complex

J Am Chem Soc. 2016 May 11;138(18):5817-20. doi: 10.1021/jacs.6b02923. Epub 2016 Apr 29.

Abstract

Proton-coupled electron-transfer reactions of phenols have received considerable attention because of their fundamental interest and their relevance to many biological processes. Here we describe a remarkable four-electron oxidation of phenols by a (salen)ruthenium(VI) complex in the presence of pyridine in CH3OH to afford (salen)ruthenium(II) p-benzoquinone imine complexes. Mechanistic studies indicate that this reaction occurs in two phases. The first phase is proposed to be a two-electron transfer process that involves electrophilic attack by Ru≡N at the phenol aromatic ring, followed by proton shift to generate a Ru(IV) p-hydroxyanilido intermediate. In the second phase the intermediate undergoes intramolecular two-electron transfer, followed by rapid deprotonation to give the Ru(II) p-benzoquinone imine product.

Publication types

  • Research Support, Non-U.S. Gov't