Abstract
Mixed-ligand oxovanadium(IV) complexes with two different types of bidentate ligands [one is dinegative O,O donor ligand (viz., glycolic acid, 2-hydroxybenzylalcohol and glycol) and the other is neutral N,N donor ligand (viz., 2,2'-bipyridine and 1,10-phenanthroline)] have been prepared and characterized by elemental analyses, IR, EPR and UV-Vis spectroscopies. The complexes are paramagnetic and showed subnormal magnetic behaviour (μ e f f = 1.01-1.60 B.M.) at RT. The V=O stretching frequencies of the complexes indicate the hexa-coordinated environment though only five donor atoms are provided to the vanadium centre and it is explained by considering the formation of bridge through either by alcoholic oxygen or by phenolic oxygen leading to dimerization. The EPR spectra support the dimeric nature of the complexes and indicate that the odd electron of the metal is present in its 3d x y orbital. The lower magnetic moment values are explained by considering the overlapping between two 3d x y orbitals of the two V 4 + ions in the dimeric complexes. The complexes display an irreversible oxidation peak in the region 0.49-0.89 V vs Ag/AgCl. μ e f f and oxidation peak potential values (E a p ) are correlated with the basicity of the donor atoms of the ligands.
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