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Sulfide oxidation by hydrogen peroxide catalyzed by iron complexes: two metal centers are better than one. 2002
Yasmina Mekmouche, and
Helga Hummel, and
Raymond Y N Ho, and
Lawrence Que, and
Volker Schünemann, and
Fabrice Thomas, and
Alfred X Trautwein, and
Colette Lebrun, and
Karine Gorgy, and
Jean-Claude Leprêtre, and
Marie-Noëlle Collomb, and
Alain Deronzier, and
Marc Fontecave, and
Stéphane Ménage
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.
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.
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