| Sumario: | 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(TMC)(OOH)]. The Mn-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 Mn-hydroperoxo species is a competent oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of sulfides. The electrophilic character of the Mn-hydroperoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles.
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