Oxovanadium(V) complexes of bis(phenolate) ligands with acetylacetone as co-ligand: Synthesis, crystal structure, electrochemical and kinetics studies on the oxidation of ascorbic acid

Abstract: Two vanadium(V) complexes, [VO(L1)](acac)] (1) and [VO(L2)(acac)] (2), where H2L1 = N,N-bis(2-hydroxy-3-5-di-tert-butylbenzyl)propylamine and H2L2 =2,2′-selenobis(4,6-di-tert-butylphenol), have been synthesized and characterized by elemental analyses, IR, 51V NMR, both in the solid and in solution, and cyclic voltammetric studies. Single crystal X-ray studies reveal that in complex 1 the vanadium atom is octahedrally coordinated with an O5N donor environment, where the oxygen atom of the VV and the N atom of the ONO ligand occupy the axial sites while two oxygen atoms (O1 and O2) from the bisphenolate ligand and two oxygen atoms (O3 and O4) from the acac ligand occupy the equatorial plane. A similar bonding pattern has also been encountered for 2 with the exception that a Se atom instead of N is involved in weak bonding to the metal center. Both complexes showed reversible cyclic voltammeric responses and E 1/2 appears at −0.18 and 0.10V versus NHE for complexes 1 and 2, respectively. The kinetics of oxidation of ascorbic acid by complex 1 were carried out in 50% MeCN–50% H2O (v/v) at 25°C. The high formation constant value, Q =63±7M−1, reveals that the reaction proceeds through the rapid formation of a H-bonded intermediate. The low k 2 Q 2/k 1 Q 1 ratio (13.4) for 1 points out that there is extensive H-bonding between the oxygen atom of the VV nd the OH group of ascorbic acid. [Copyright &y& Elsevier]