Electrochemical investigations of oxovanadium(IV) complexes with bidentate Schiff base ligands in dimethylformamide
JOURNAL OF THE INDIAN CHEMICAL SOCIETY(2009)
Abstract
The electrochemical redox properties of bidentate Schiff base oxovanadium(IV) complexes viz. VO(sal-anl)(2) 1, VO(sal-tod)(2) 2, VO(hmp-and)(2) 3 and VO(hmp-oxime)(2) 4 have been studied In DMF/0.1 M TBAP using cyclic voltammetry at a Pt-working electrode. The electrochemistry of sal-ani and sal-tod ligands was also examined for the sake of comparison. Complexes 1 and 2 show almost similar electrochemistry. Oxidation of complex 2 is easier while reduction is difficult in comparison to 1 due to the +I inductive effect of electron-donating methyl group at the para position of toluidine. Complex 1 showed two irreversible anodic waves at E-pa1 = +0.68 V and E-pa2 = + 1.06 V vs SCE and two irreversible cathodic peaks at E-pc1 -0.90 V and E-pc2 = -1.325 V vs SCE followed by an irreversible anodic peak at E-pa2 = -0.42 V at scan rate 100 mV s(-1). On the basis of CV results, it is concluded that in complexes 1 and 2, the redox processes a(1) and c(2) are metal-based while the redox processes a(2) and c(1), seem to be ligand-based. The CVs of 3 and 4 are also qualitatively similar. It is noteworthy that the anodic peak potential for the process VO2+/3+ shifted to more positive values in the sequence : VO(sal-tod)(2) -> VO(sal-anl)(2) -> VO(hmp-oxime)(2) -> VO(hmp-and)(2).
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Key words
Cyclic voltammetry,electrochemistry,Schiff bases,vanadium complexes,biomimetic
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