Chemistry. 2002 Mar 1;8(5):1196-204.

Sulfide oxidation by hydrogen peroxide catalyzed by iron complexes: two metal centers are better than one.

Mekmouche Y, Hummel H, Ho RY, Que L Jr, Schünemann V, Thomas F, Trautwein AX, Lebrun C, Gorgy K, Leprêtre JC, Collomb MN, Deronzier A, Fontecave M, Ménage S.

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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.

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.

PMID:: 11891908; [PubMed - indexed for MEDLINE]

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