Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(III)-Hydroperoxo Complex

Abstract

We report the first example of a mononuclear nonheme manganese(III)- hydroperoxo complex derived from protonation of an isolated manganese(III)- peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn III(TMC)(OOH)]2+. The MnIII-hydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the binding of a hydroperoxide ligand in an end-on fashion. The MnIII-hydroperoxo species is a competent oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of sulfides. The electrophilic character of the Mn III-hydroperoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles. © 2014 American Chemical Society.