A new binuclear oxovanadium(V) complex as a catalyst in combination with pyrazinecarboxylic acid (PCA) for efficient alkane oxygenation by H2O2

A new binuclear oxovanadium(V) complex [{VO(OEt)(EtOH)}(2)L] (1) where H4L is bis(2-hydroxybenzylidene)terephthalohydrazide has been synthesized and fully characterized. The combination of 1 with pyrazine-2-carboxylic acid (PCA; a cocatalyst) affords a catalytic system for the efficient oxidation of saturated hydrocarbons, RH, with hydrogen peroxide and air in acetonitrile solution at 50 degrees C to produce alkyl hydroperoxides, ROOH, as the main primary products. Very high turnover numbers (TONs) have been attained in this reaction: for example, after 2220 min, TON = 44 000 and initial TOF (turnover frequency) = 3300 h(-1) per molecule of complex 1. The estimated activation energy of the cyclohexane oxygenation in the presence of 1/PCA is E-a = 16 +/- 2 kcal mol(-1). This value is identical to that obtained for the cyclohexane oxidation with H2O2 catalyzed by the (n-Bu4N)[VO3]/PCA combination (17 +/- 2 kcal mol(-1)). The dependences of initial oxidation rates W-0 on the initial concentrations of all components of the reaction mixture have been determined. Based on these kinetic data and on the regio- and bond-selectivity parameters measured in the oxidation of linear and branched alkanes a mechanism of the oxidation has been proposed which includes the generation of hydroxyl radicals in the crucial stage.