Kinetics of oxidation of thioethers, alkenes, and sulfoxides by tetrahexylammonium tetrakis(diperoxomolybdo)phosphate (TEAM) were performed in chloroform. The results obtained, compared with the corresponding data of a series of Mo(VI) peroxo complexes, rule out a nucleophilic oxygen transfer mechanism. Rather, the data point to Mo(VI) peroxopolyoxo complexes as well as simple peroxo complexes behave as electrophilic oxidants toward nucleophilic substrates such as thioethers and alkenes. A study of the countercation effects indicates that 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(diperoxomolybdo)phosphate
Ballistreri, F. P.;Bazzo, A.;TOMASELLI, Gaetano;
1992
Abstract
Kinetics of oxidation of thioethers, alkenes, and sulfoxides by tetrahexylammonium tetrakis(diperoxomolybdo)phosphate (TEAM) were performed in chloroform. The results obtained, compared with the corresponding data of a series of Mo(VI) peroxo complexes, rule out a nucleophilic oxygen transfer mechanism. Rather, the data point to Mo(VI) peroxopolyoxo complexes as well as simple peroxo complexes behave as electrophilic oxidants toward nucleophilic substrates such as thioethers and alkenes. A study of the countercation effects indicates that 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.