title: 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 Mn(III)-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(III)-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.
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University , Seoul 120-750, Korea.
authors.forename: Hee
authors.initials: H
authors.lastname: So
authors.forename: Young Jun
authors.initials: YJ
authors.lastname: Park
authors.forename: Kyung-Bin
authors.initials: KB
authors.lastname: Cho
authors.forename: Yong-Min
authors.initials: YM
authors.lastname: Lee
authors.forename: Mi Sook
authors.initials: MS
authors.lastname: Seo
authors.forename: Jaeheung
authors.initials: J
authors.lastname: Cho
authors.forename: Ritimukta
authors.initials: R
authors.lastname: Sarangi
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry*; D008024:Ligands; D008345:Manganese / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D013440:Sulfides / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D006571:Heterocyclic Compounds; D008024:Ligands; D016877:Oxidants; D013440:Sulfides; C024560:cyclam; D008345:Manganese; C093850:methylphenylsulfide; D006861:Hydrogen Peroxide