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.

العنوان

Transition Metal Chemistry

الناشر

springer

بلد الناشر

ألمانيا

Indexing

Thomson Reuters

معامل التأثير

1,465

نوع المنشور

مطبوع فقط

المجلد

29

السنة

2004

الصفحات

91–95