Although pentamethylene sulfide (tetrahydrothiopyran) lacks acidic hydrogen, Os^VIII has been found to catalyze its oxidation by alkaline K₃Fe(CN)₆to 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, K ₄Fe(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.

Title

Transition Metal Chemistry

Publisher

springer

Publisher Country

Germany

Indexing

Thomson Reuters

Impact Factor

1.465

Publication Type

Prtinted only

Volume

29

Year

2004

Pages

91–95