Mechanism of oxygen transfer from the vanadium(V) complexes with ligands O2 2- and O3 2-

The oxygen transfer from the vanadium(V) complexes containing peroxo, oxo, and ozonide ligands to electron-donating substrates (ethylene and vinyl methyl ether) was studied in the framework of the DFT with the M06 hybrid functional. The O atom of the ozonide fragment in the O3VO(η-O2)- complex is transferred to the electron-donating substrates with lower energy expenses than the O atom of the peroxo group of the isomeric triperoxo complex, in spite of the fact that the presence of the peroxo group in the ozonide complexes stabilizes it favoring the formation of the V-Oc bond according to the data of topological analysis of the electron density in terms of the theory of atoms in molecules (AIM). The calculation results are in agreement with the experimental kinetic data indicating somewhat lower reactivity of triperoxovanadate compared to the isomeric oxygenyl complexes. © 2014 Springer Science+Business Media New York.