Mechanism of oxygen transfer from the vanadium(v) complexes with ligands O-2(2-) and O-3(2-)

作者：Markov A A^*; Sharifullina G F; Dolin S P; Moiseeva N I; Gekhman A E; Moiseev I I

来源：Russian Chemical Bulletin, 2014, 63(6): 1283-1288.

DOI：10.1007/s11172-014-0591-x

• quantum chemical calculations
• DFT
• M06 functional
• quantum theory of atoms in molecules (QTAIM)
• epoxidation
• olefins
• peroxo compounds
• vanadium

The oxygen transfer from the vanadium(v) complexes containing peroxo, oxo, and ozorficle 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(eta-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-Or 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 triper-oxovanadate compared to the isomeric oxygenyl complexes.

• 出版日期2014-6