| Abstract |
Five monomeric oxovanadium(V) complexes [VO(OMe)((NO)-O-boolean AND)(2)] with the nitro or halogen substituted quinolin-8-olate ligands were synthesized and characterized using Fourier transform infrared, H-1 and C-13 NMR, high-resolution mass spectrornetry electrospray ionization as well as X-ray diffraction and UV-vis spectroscopy. These complexes exhibit high catalytic activity toward oxidation of inert alkanes to alkyl hydroperoxides by H2O2 in aqueous acetonitrile with the yield of oxygenate products up to 39\% and turnover number 1780 for 1 h. The experimental kinetic study, the C6D12 and O-18(2) labeled experiments, and density functional theory (DFT) calculations allowed to propose the reaction mechanism, which includes the formation of HO center dot radicals as active oxidizing species. The mechanism of the HO center dot formation appears to be different from those usually accepted for the Fenton or Fenton-like systems. The activation of H2O2 toward homolysis occurs upon simple coordination of hydrogen peroxide to the metal center of the catalyst molecule and does not require the change of the metal oxidation state and formation of the HOO center dot radical. Such an activation is associated with the redox-active nature of the quinolin-8-olate ligands. The experimentally determined activation energy for the oxidation of cyclohexane with complex [VO(OCH3)(5-Cl-quin)(2)] (quin = quinolin-8-olate) is 23 +/- 3 kcal/mol correlating well with the estimate obtained from the DFT calculations. |
