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.
Reactivity of Peroxopolyoxo Complexes. Oxidation of Thioethers, Alkenes, and Sulfoxides by Tetrahexylammonium Tetrakis( diperoxomo1ybdo)p hosp hate
F. P. Ballistreri;A. Bazzo;G. A. Tomaselli;Toscano R
1992-01-01
Abstract
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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
