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

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.