Synthesis, characterization, DFT calculations, and catalytic epoxidation of two oxovanadium(IV) Schiff base complexes

Abstract

The present paper reports the synthesis, characterization, and DFT calculations of two oxovanadium (IV) Schiff base complexes symbolized as VOL1 and VOL2, which prepared by the reaction of bivalent tridentate Schiff base ligands (E)-2-((5-chloro-2-hydroxybenzylidene)amino)acetic acid and (E)-2-((2-hydoxy-5-nitrobenzylidene)amino)acetic acid and VO(acac)2 as vanadium source. The Schiff base ligands and its oxovanadium (IV) complexes were characterized by the elemental analysis (C, H, N), FTIR, 1 H NMR and 13 C NMR, DFT calculations were performed to derive some of their molecular properties. Schiff base ligands coordinated to vanadium center via nitrogen from the azomethine group and one oxygen from the hydroxyl attached to the benzene ring and one oxygen from hydroxyl of carboxyl group. The catalytic activity of the two complexes were tested against cyclooctene and found that both complexes were highly effective and selective in optimized conditions when used as cyclooctene epoxidation catalysts with the conversion percentage of 91.85% (with VOL1) and 87.40% (with VOL2) at 78 °C within a period of ten hours. To understand the structural properties of the two complexes, the two complexes were well optimized at B3LYP/6-31G(d,p) level of theory, structural parameters such as electron affinity, global electrophilicity, global hardness, electronegativity, ionization potential, and electron chemical potential based on HOMO and LUMO energy values were calculated.