title: Dioxygen activation by mononuclear nonheme iron(II) complexes generates iron-oxygen intermediates in the presence of an NADH analogue and proton.
abstract: One primary goal in biomimetic research is to understand mechanisms of dioxygen activation, structures of reactive intermediates, and reactivities of the intermediates involved in catalytic oxidation reactions by metalloenzymes, such as heme and nonheme iron oxygenases. In this communication, we have reported the first example of generating nonheme iron(III)-hydroperoxo and iron(IV)-oxo complexes by activating O(2) with a biologically important electron donor, an NADH analogue, and an acid. The formation of iron(III)-hydroperoxo and iron(IV)-oxo complexes was found to depend on the supporting ligands. We have also demonstrated that high-spin nonheme iron(II) complexes with a low oxidation potential are able to bind and activate O(2) to generate the iron-oxygen intermediates.
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea.
authors.forename: Seungwoo
authors.initials: S
authors.lastname: Hong
authors.forename: Yong-Min
authors.initials: YM
authors.lastname: Lee
authors.forename: Woonsup
authors.initials: W
authors.lastname: Shin
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
mesh_terms: D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D009243:NAD / Q000031:analogs & derivatives* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*
chemical_list: D009243:NAD; D007501:Iron; D010100:Oxygen