title: Sulfide oxidation by hydrogen peroxide catalyzed by iron complexes: two metal centers are better than one.
abstract: Peroxoiron species have been proposed to be involved in catalytic cycles of iron-dependent oxygenases and in some cases as the active intermediates during oxygen-transfer reactions. The catalytic properties of a mononuclear iron complex, [Fe(II)(pb)(2)(CH(3)CN)(2)] (pb=(-)4,5-pinene-2,2'-bipyridine), have been compared to those of its related dinuclear analogue. Each system generates specific peroxo adducts, which are responsible for the oxidation of sulfides to sulfoxides. The dinuclear catalyst was found to be more reactive and (enantio)selective than its mononuclear counterpart, suggesting that a second metal site affords specific advantages for stereoselective catalysis. These results might help for the design of future enantioselective iron catalysts.
authors.affiliation: Laboratoire de Chimie et Biochimie, Centres Rédox Biologiques, Université Joseph Fourier/DBMS/CEA, UMR CNRS 5047 Grenoble, 17 rue des Martyrs, 38054 Grenoble Cédex 9, France.
authors.forename: Yasmina
authors.initials: Y
authors.lastname: Mekmouche
authors.forename: Helga
authors.initials: H
authors.lastname: Hummel
authors.forename: Raymond Y N
authors.initials: RY
authors.lastname: Ho
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
authors.forename: Volker
authors.initials: V
authors.lastname: Schünemann
authors.forename: Fabrice
authors.initials: F
authors.lastname: Thomas
authors.forename: Alfred X
authors.initials: AX
authors.lastname: Trautwein
authors.forename: Colette
authors.initials: C
authors.lastname: Lebrun
authors.forename: Karine
authors.initials: K
authors.lastname: Gorgy
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Leprêtre
authors.forename: Marie-Noëlle
authors.initials: MN
authors.lastname: Collomb
authors.forename: Alain
authors.initials: A
authors.lastname: Deronzier
authors.forename: Marc
authors.initials: M
authors.lastname: Fontecave
authors.forename: Stéphane
authors.initials: S
authors.lastname: Ménage
mesh_terms: D002384:Catalysis; D006861:Hydrogen Peroxide / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013440:Sulfides / Q000737:chemistry*; D013454:Sulfoxides / Q000737:chemistry
chemical_list: D013440:Sulfides; D013454:Sulfoxides; D006861:Hydrogen Peroxide; D007501:Iron