title: A new binuclear oxovanadium(V) complex as a catalyst in combination with pyrazinecarboxylic acid (PCA) for efficient alkane oxygenation by H2O2.
abstract: A new binuclear oxovanadium(V) complex [{VO(OEt)(EtOH)}2L] (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 °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 W0 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.
authors: Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisboa, Portugal.
authors: Manas
authors: M
authors: Sutradhar
authors: Nikita V
authors: NV
authors: Shvydkiy
authors: M Fátima C
authors: MF
authors: Guedes da Silva
authors: Marina V
authors: MV
authors: Kirillova
authors: Yuriy N
authors: YN
authors: Kozlov
authors: Armando J L
authors: AJ
authors: Pombeiro
authors: Georgiy B
authors: GB
authors: Shul'pin
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D002384:Catalysis; D006861:Hydrogen Peroxide / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011718:Pyrazinamide / Q000031:analogs & derivatives* / Q000737:chemistry; D014639:Vanadium / Q000737:chemistry*
chemical_list: D000473:Alkanes; D009942:Organometallic Compounds; D014639:Vanadium; D011718:Pyrazinamide; C005296:pyrazinoic acid; D017665:Hydroxyl Radical; D006861:Hydrogen Peroxide; D010100:Oxygen