Results concerning oxidn. processes of thioethers, alkenes, sulfoxides and amines by Mo(VI) and W(VI) polyperoxo complexes are reported. The data, compared with those obtained for the corresponding mononuclear complexes, seem to rule out a nucleophilic oxygen transfer mechanism. Rather they indicate that polyperoxo complexes as well as mononuclear peroxo complexes behave as electrophilic oxidants toward nucleophilic substrates such as thioethers and alkenes. The bulkiness of the oxidant countercation affects the reactivity of the peroxo complex itself. With sulfoxides the mechanistic picture is less conclusive, whereas oxidn. of secondary amines to nitrones appears a complex reaction in which radicals can play a relevant role.

The course of oxidation processes of organic substrates mediated by Mo(VI) and W(VI) polyoxoperoxo complexes

BALLISTRERI, Francesco Paolo;TOMASELLI, Gaetano;TOSCANO, Rosa Maria
1995-01-01

Abstract

Results concerning oxidn. processes of thioethers, alkenes, sulfoxides and amines by Mo(VI) and W(VI) polyperoxo complexes are reported. The data, compared with those obtained for the corresponding mononuclear complexes, seem to rule out a nucleophilic oxygen transfer mechanism. Rather they indicate that polyperoxo complexes as well as mononuclear peroxo complexes behave as electrophilic oxidants toward nucleophilic substrates such as thioethers and alkenes. The bulkiness of the oxidant countercation affects the reactivity of the peroxo complex itself. With sulfoxides the mechanistic picture is less conclusive, whereas oxidn. of secondary amines to nitrones appears a complex reaction in which radicals can play a relevant role.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11769/14418
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