Although pentamethylene sulfide (tetrahydrothiopyran) lacks acidic hydrogen, Os-VIII has been found to catalyze its oxidation by alkaline K3Fe(CN)(6) to produce 3-hydroxypentamethylene sulfide as the only product. The kinetics reveal first-order dependence on ferricyanide and Os-VIII, and zero order on pentamethylene sulfide and OH-. The effects of introduced electrolytes, K4Fe(CN)(6), relative permittivity and temperature have also been studied. On the basis of kinetic evidence, a mechanism that involves anation of the osmium catalyst (sulfide/water interchange) followed by intramolecular proton abstraction, followed by an electron transfer step has been proposed and discussed.

TRANSITION METAL CHEMISTRY    Volume: 29    Issue: 1    Pages: 91-95    Published: FEB 2004