title: A mononuclear non-heme high-spin iron(III)-hydroperoxo complex as an active oxidant in sulfoxidation reactions.
abstract: We report the first direct experimental evidence showing that a high-spin iron(III)-hydroperoxo complex bearing an N-methylated cyclam ligand can oxidize thioanisoles. DFT calculations showed that the reaction pathway involves heterolytic O-O bond cleavage and that the choice of the heterolytic pathway versus the homolytic pathway is dependent on the spin state and the number of electrons in the d(xz) orbital of the Fe(III)-OOH species.
authors.affiliation: Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea.
authors.forename: Yun Mi
authors.initials: YM
authors.lastname: Kim
authors.forename: Kyung-Bin
authors.initials: KB
authors.lastname: Cho
authors.forename: Jaeheung
authors.initials: J
authors.lastname: Cho
authors.forename: Binju
authors.initials: B
authors.lastname: Wang
authors.forename: Chunsen
authors.initials: C
authors.lastname: Li
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
mesh_terms: D005290:Ferric Compounds / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry; D008958:Models, Molecular; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D010545:Peroxides / Q000737:chemistry; D013440:Sulfides / Q000737:chemistry*
chemical_list: D005290:Ferric Compounds; D006571:Heterocyclic Compounds; D016877:Oxidants; D010545:Peroxides; D013440:Sulfides; C024560:cyclam; C093850:methylphenylsulfide