Reactivity of Peroxopolyoxocomplexes. Oxidation of Thioethers, Alkenes and Sulfoxides by Tetrahexilammonium Tetrakis (Diperoxomolybdo) Phosphate.

Kinetics of oxidation of thioethers, alkenes, and sulfoxides by tetrahexylammonium tetrakis(diperoxomo1ybdo)phaephate (TEAM) were performed in chloroform. The results obtained, compared with the correapondingdata of a series of Mo(V1) peroxo complexes, rule out a nucleophilic oxygen transfer mechanism. Rather, thedata point to Mo(VI) peroxopolyoxo complexes as well as simple peroxo complexes behave as electrophilic oxidantstoward nucleophilic substrates such as thioethers and alkenes. A study of the countercation effects indicatesthat the increasing bulkiness of the cation reduces the electrophilicity of the peroxopolyoxo complex. With sulfoxides,incursion of SET processes might be a likely event.