Synthesis, characterization and reactivity of trinuclear Cu(II) complexes derived from disalicylaldehyde malonoyldihydrazone

Three new homotrinuclear copper(II) complexes [Cu-3(slmh)(mu-Cl)(2)(CH3OH)(3)]center dot 0.5CH(3)OH (1), [Cu-3(slmh)(NO3)(2)(CH3OH)(5)]center dot 1.5CH(3)OH (2) and [Cu-3(slmh)(mu-ClO4)(2)(CH3OH)(3)]center dot 2CH(3)OH (3) from disalicylaldehyde malonoyldihydrazone have been synthesized and characterized. The composition of the complexes has been established on the basis of data obtained from analytical and thermoanalytical data. The structure of the complexes has been discussed in the light of molar conductance, electronic, FT-IR and far-IR spectral data, magnetic moment and EPR spectral studies. The molar conductance values for the complexes in DMSO solution indicate that all of them are non-electrolyte. The magnetic moment values for the complexes suggest considerable metal-metal intramolecular interaction between metal ions in the structural unit of the complexes. The EPR spectral features reveal that at RT, the ground state for the complexes is a mixture of the quartet state (S = 3/2) and doublet state (S = 1/2). At lower temperature, the ground state for the complexes is d(x)(y)(2)(2) with considerable contribution from d(z)(2) orbital. Dihydrazone ligand is present in enol form in all of the complexes. The complexes have distorted square pyramidal stereochemistry. The electron transfer reactions of the complexes have been investigated by cyclic voltammetry. Hydrogen peroxide mediated oxidation of benzyl alcohol catalyzed by complex 1 has been studied. (C) 2014 Elsevier B.V. All rights reserved.