Mechanistic investigation of the catalytic system based on N-hydroxy-phthalimide with vanadium co-catalysts for aerobic oxidation of alcohols with dioxygen
2009; Elsevier BV; Volume: 263; Issue: 1 Linguagem: Inglês
10.1016/j.jcat.2009.02.007
ISSN1090-2694
Autores Tópico(s)Metal-Catalyzed Oxygenation Mechanisms
Resumo[n-Bu4N]VO3 or a combination of vanadium complexes with some additives, as chloride salts or amines, are attractive and effective co-catalysts for aerobic oxidation of alcohols with dioxygen catalyzed by N-hydroxyphthalimide (NHPI). The role of the additives relates to the formation of more labile six co-ordinate vanadium complexes. A mechanism for the aerobic oxidation of alcohols with dioxygen is proposed and its essential steps are the formation of oxotrialkoxyvanadium(V) complexes and generation of a phthalimide-N-oxyl (PINO•) radical as result of reaction of NHPI with oxovanadium(V) compounds. The oxidation of alcohols concerns to both radical and molecular pathways.
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