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Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(III)-Hydroperoxo Complex
- Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(III)-Hydroperoxo Complex
- So, H[So, Hee]; Park, YJ[Park, Young Jun]; Cho, KB[Cho, Kyung-Bin]; Lee, YM[Lee, Yong-Min]; Seo, MS[Seo, Mi Sook]; Cho, J[Cho, Jaeheung]; Sarangi, R[Sarangi, Ritimukta]; Nam, W[Nam, Wonwoo]
- DGIST Authors
- Cho, J[Cho, Jaeheung]
- Issue Date
- Journal of the American Chemical Society, 136(35), 12229-12232
- Article Type
- Chemistry; Coordination Complexes; Coordination Compound; Cyclam; Heterocyclic Compound; Heterocyclic Compounds; Hydrogen Peroxide; Ligand; Ligands; Manganese; Methylphenylsulfide; Oxidants; Oxidation-Reduction; Oxidation-Reduction Reaction; Oxidizing Agent; Sulfide; Sulfides
- 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.
- American Chemical Society
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