Mononuclear Oxidovanadium(IV) Complexes with BIAN Ligands: Synthesis and Catalytic Activity in the Oxidation of Hydrocarbons and Alcohols with Peroxides

Reactions of VCl3 with 1,2-Bis[(4-methylphenyl)imino]acenaphthene (4-Me-C6H4-bian) or 1,2-Bis[(2-methylphenyl)imino]acenaphthene (2-Me-C6H4-bian) in air lead to the formation of [VOCl2(R-bian)(H2O)] (R = 4-Me-C6H4 (1), 2-Me-C6H4 (2)). Thes complexes were characterized by IR and EPR spectroscopy as well as elemental analysis. Complexes 1 and 2 have high catalytic activity in the oxidation of hydrocarbons with hydrogen peroxide and alcohols with tert-butyl hydroperoxide in acetonitrile at 50 °С. The product yields are up to 40% for cyclohexane. Of particular importance is the addition of 2-pyrazinecarboxylic acid (PCA) as a co-catalyst. Oxidation proceeds mainly with the participation of free hydroxyl radicals, as evidenced by taking into account the regio- and bond-selectivity in the oxidation of n-heptane and methylcyclohexane, as well as the dependence of the reaction rate on the initial concentration of cyclohexane.