Both oxido and non-oxido vanadium complexes with a diversity of N- and/or O-ligands have been disclosed as effective catalysts towards the development of sustainable catalytic processes of industrial significance, and selected systems studied in the author laboratory are discussed. The role played by the ligand and its cooperation with the metal in the catalytic cycle are highlighted for the following types of oxidation catalytic reactions: - Peroxidative oxidation of alkanes to alcohols and ketones; - Water oxidation to hydrogen peroxide and dioxygen; - Thiols oxidation to organodisulfides. The catalysts can be mono- or multinuclear vanadium complexes and include water soluble ones with a diversity of ligands, namely polydentate and with hemilabile character. Such ligands can be redox active and bear azine-type fragments or the N-hydroxyimino moiety. The latter are N-hydroxyiminodicarboxylates, a type that is found in Amavadin (a natural bare vanadium complex present in some Amanita toadstools) and its models, i.e., [V(HIDPA)2]2- (HIDPA = basic form of N-hydroxyiminodipropionic acid) and [V(HIDA)2]2- (HIDA = basic form of N-hydroxyiminodiacetic acid), respectively. The roles of related ligands and of water are also discussed, as well as the use of unconventional conditions, such as solvent-free, microwave irradiation and mechanochemical methods which can favour the sustainability of the processes.

Vanadium complexes in oxidation catalysis: Metal-ligand cooperation

2019 Spring National Meeting

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