Osmium(VIII)-Catalyzed Oxidation of Pentamethylene Sulfide

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Journal Title, Volume, Page: 
Transition Metal Chemistry February 2004, Volume 29, Issue 1, pp 91-95
Year of Publication: 
2004
Authors: 
Mohammed M. Al-Subu
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Current Affiliation: 
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Preferred Abstract (Original): 

Although pentamethylene sulfide (tetrahydrothiopyran) lacks acidic hydrogen, OsVIII 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 OsVIII, 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.

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