Spectroscopic characterization and reactivity studies of a mononuclear nonheme Mn(III)-hydroperoxo complex

Hee So, Young Jun Park, Kyung Bin Cho, Yong Min Lee, Mi Sook Seo, Jaeheung Cho, Ritimukta Sarangi, Wonwoo Nam

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37 Scopus citations

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.

Original languageEnglish
Pages (from-to)12229-12232
Number of pages4
JournalJournal of the American Chemical Society
Volume136
Issue number35
DOIs
StatePublished - 3 Sep 2014

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