title: Demonstration of the heterolytic O-O bond cleavage of putative nonheme iron(II)-OOH(R) complexes for Fenton and enzymatic reactions.
abstract: One-electron reduction of mononuclear nonheme iron(III) hydroperoxo (Fe(III)-OOH) and iron(III) alkylperoxo (Fe(III)-OOR) complexes by ferrocene (Fc) derivatives resulted in the formation of the corresponding iron(IV) oxo complexes. The conversion rates were dependent on the concentration and oxidation potentials of the electron donors, thus indicating that the reduction of the iron(III) (hydro/alkyl)peroxo complexes to their one-electron reduced iron(II) (hydro/alkyl)peroxo species is the rate-determining step, followed by the heterolytic O-O bond cleavage of the putative iron(II) (hydro/alkyl)peroxo species to give the iron(IV) oxo complexes. Product analysis supported the heterolytic O-O bond-cleavage mechanism. The present results provide the first example showing the one-electron reduction of iron(III) (hydro/alkyl)peroxo complexes and the heterolytic O-O bond cleavage of iron(II) (hydro/alkyl)peroxo species to form iron(IV) oxo intermediates which occur in nonheme iron enzymatic and Fenton reactions.
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750 (Korea).
authors.forename: Suhee
authors.initials: S
authors.lastname: Bang
authors.forename: Sora
authors.initials: S
authors.lastname: Park
authors.forename: Yong-Min
authors.initials: YM
authors.lastname: Lee
authors.forename: Seungwoo
authors.initials: S
authors.lastname: Hong
authors.forename: Kyung-Bin
authors.initials: KB
authors.lastname: Cho
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
mesh_terms: D015393:Chemistry, Bioinorganic; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D007501:Iron
keywords: bioinorganic chemistry; enzyme models; iron; nonheme compounds; reaction mechanisms