Enantioselective Sulfoxidation as a Probe for a Metal-Based Mechanism in H(2)O(2)-Dependent Oxidations Catalyzed by a Diiron Complex.

The catalytic properties of the diiron complex 1, Fe(2)OL(4)(H(2)O)(2)(ClO(4))(4) with L = (-)-4,5-pinenebipyridine, a chiral bipyridine derivative, have been investigated. Complex 1 efficiently catalyzes the oxidation of aryl sulfides to the corresponding sulfoxides by hydrogen peroxide, with yields ranging from 45 to 90% based on the oxidant. Furthermore the reactions were enantioselective and produced a mixture of sulfoxide enantiomers with significant enantiomeric excesses.

H O -Dependent Fe-Catalyzed Oxidations: Control of the Active Species.

Manipulation of the coordination sphere of an Fe ion can be used to tune the balance between different catalytic pathways for oxidation (OH versus iron-based oxidant; see scheme). This reinvestigation of Fenton chemistry uses the iron complex shown as a mechanistic probe.