Peroxidative Oxidation of Alkanes and Alcohols under Mild Conditions by Di- and Tetranuclear Copper (II) Complexes of Bis (2-Hydroxybenzylidene) Isophthalohydrazide

Bis(2-hydroxybenzylidene)isophthalohydrazide (H(4)L) has been used to synthesize the dinuclear [Cu(2)(1κNO(2):2κN′O′(2)-H(2)L)(NO(3))(2)(H(2)O)(2)] (1) and the tetranuclear [Cu(4)(μ-1κNO(2):2κN′O(2)-H(2)L)(2)(μ-NO(3))(2)(H(2)O)(4)]·2C(2)H(5)OH (2) complexes. The solvent plays an important role in determining the ligand behaviour in the syntheses of the complexes. An ethanol-acetonitrile mixture of solvents favours partials enolization in the case of 2. Both complexes have been characterized by elemental analysis, infrared radiation (IR), single crystal X-ray crystallography and electrochemical methods. The variable temperature magnetic susceptibility measurements of 2 show strong antiferromagnetic coupling between the central nitrato-bridged Cu (II) ions. The catalytic activity of both 1 and 2 has been screened toward the solvent-free microwave-assisted oxidation of alcohols and the peroxidative oxidation of alkanes under mild conditions. Complex 1 exhibits the highest activity for both oxidation reactions, leading selectively to a maximum product yield of 99% (for the 1-phenylethanol oxidation after 1 h without any additive) and 13% (for the cyclohexane oxidation to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone after 3 h).