Chapter 5: Peroxo-vanadium Complexes as Sustainable Catalysts in Oxidations, Halogenations and Other Organic Transformations

Vanadium in its high-oxidation state can activate hydrogen peroxide and other alkyl hydroperoxides, generating highly active oxidising species, namely vanadium peroxido-complexes. Several studies have been performed to deeply investigate structural features and reactivity of such species. In this chapter, the application of V-peroxido-complexes in oxidation and halogenation reactions will be discussed. Specifically, oxidation of different hydrocarbon substrates (i.e., alkanes, alkenes, aromatics), alcohols, phenols and sulphides, as well as the catalytic bromination reaction of diverse organic substrates will be addressed. Notably, vanadium peroxido-complexes result in effective catalysts to perform these transformations in very mild conditions. Importantly, the feasibility of the proposed procedures on a large scale allows their exploitation for appealing applicative purposes. Examples of lignin valorisation, fuel desulfurization, as well as clean synthetic methodologies for developing interesting building blocks for synthetic, industrial and pharmaceutic applications will be summarised.