Issue 57, 2019

Aromatic hydroxylation of anthracene derivatives by a chromium(iii)-superoxo complex via proton-coupled electron transfer

Abstract

The chemistry of metal-superoxo intermediates started being unveiled in oxidation reactions by enzymes and their synthetic model compounds. However, aromatic hydroxylation reactions by the metal-superoxo species are yet to be demonstrated. In this study, we report for the first time that the hydroxylation of aromatic compounds such as anthracene and its derivatives by a mononuclear nonheme Cr(III)-superoxo complex, [(Cl)(TMC)CrIII(O2)]+ (1), occurs in the presence of triflic acid (HOTf) via the rate-determining proton-coupled electron transfer (PCET) from anthracene to 1, followed by a fast further oxidation to give anthraquinone. The rate constants of electron transfer from anthracene derivatives to 1 in the presence of HOTf are well analyzed in light of the Marcus theory of electron transfer.

Graphical abstract: Aromatic hydroxylation of anthracene derivatives by a chromium(iii)-superoxo complex via proton-coupled electron transfer

Supplementary files

Article information

Article type
Communication
Submitted
26 Apr 2019
Accepted
20 Jun 2019
First published
24 Jun 2019

Chem. Commun., 2019,55, 8286-8289

Author version available

Aromatic hydroxylation of anthracene derivatives by a chromium(III)-superoxo complex via proton-coupled electron transfer

T. Devi, Y. Lee, W. Nam and S. Fukuzumi, Chem. Commun., 2019, 55, 8286 DOI: 10.1039/C9CC03245B

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