期刊
TRANSITION METAL CHEMISTRY
卷 30, 期 4, 页码 471-480出版社
SPRINGER
DOI: 10.1007/s11243-005-0414-x
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Four new picolyl hydrazones were prepared via Schiff-base condensation of picolonic acid hydrazide with alpha-formyl-(L-1), alpha-acetyl-(L-2), alpha-benzoyl-(L-3) pyridine and alpha-formyl-(L-4) thiophene. Copper(II) complexes of these hydrazones and a series of copper(II) complexes containing (L-2) and various anions (Cl, Br, NO3, SCN, SO4, ClO4, AcO, PF6 and BF4) have been synthesized. Elemental, thermal analysis, molar conductivity, magnetic moment measurements and spectral (i.r., electronic and e.s.r.) studies have been used to characterize the prepared compounds. The overall structure and reactivity of the reported copper(II) chelates critically depend on the ligand structure and the nature of counter anion incorporated in the complex molecule. Octahedral [complex (7)], square-pyramidal [complex (8)] and square-planar monomeric species [complexes (1-6), (9) and (10)] and a dimeric structure with oxygen bridge in square-planar geometry [complexes (11) and (12)] were suggested. The reported copper(II) complexes exhibit promising oxidase catalytic activity towards the aerobic oxidation of vitamin C. A linear correlation exists between the oxidase catalytic activity and the Lewis-acidity of the central copper(II) ion created by the donating properties of the parent ligand, as well the irregularity of the coordination environment. The probable mechanistic implications of the catalytic oxidation reactions are discussed.
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