Synthesis, Characterization, X‑ray Crystal Structure, DFT Calculations, and Catalytic Properties of a Dioxidovanadium(V) Complex Derived from Oxamohydrazide and Pyridoxal: A Model Complex of Vanadate-Dependent Bromoperoxidase

A vanadium­(V) complex with the formula [Et₃NH]­[V^VO₂(sox-pydx)] with a new tridentate ligand 2-[2-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]­methylene]­hydrazinyl]-2-oxoacetamide (soxH-pydxH), obtained by condensation of oxamohydrazide and pyridoxal (one of the forms of vitamin B₆), has been synthesized. The compound was characterized by various analytical and spectroscopic methods, and its structure was determined by single-crystal X-ray diffraction technique. Density functional theory (DFT) and time-dependent DFT calculations were used to understand the electronic structure of the complex and nature of the electronic transitions observed in UV–vis spectra. In the complex, vanadium­(V) is found to be pentacoordinated with two oxido ligands and a bianionic tridentate ONO-donor ligand. The vanadium center has square-pyramidal geometry with an axial oxido ligand, and the equatorial positions are occupied by another oxido ligand and a phenolato oxygen, an imine nitrogen, and a deprotonated amide oxygen of the hydrazone ligand. A DFT-optimized structure of the complex shows very similar metrical parameters as determined by X-ray crystallography. The O₄N coordination environment of vanadium and the hydrogen-bonding abilities of the pendant amide moiety have a strong resemblance with the vanadium center in bromoperoxidase enzyme. Bromination experiments using H₂O₂ as the oxidizing agent, with model substrate phenol red, and the vanadium complex as a catalyst show a remarkably high value of k_cat equal to 26340 h^–1. The vanadium compound also efficiently catalyzes bromination of phenol and salicylaldehyde as well as oxidation of benzene to phenol by H₂O₂.