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

Abstract

A vanadium(V) complex with the formula [Et3NH][V(V)O2(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 kcat equal to 26,340 h(-1). The vanadium compound also efficiently catalyzes bromination of phenol and salicylaldehyde as well as oxidation of benzene to phenol by H2O2.

4,6‐Diacetyl Resorcinol Based Vanadium(V) Complexes: Reactivity and Catalytic Applications

“…All the ligands exhibit one peak at ca. +1.0 V, which has been attributed to hydrazine‐based ligand oxidation . Furthermore, in the cyclic voltammograms of all the complexes, a reductive response at ca.…”

Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis

“…[10] Bromoperoxidases as catalysts for oxidative bromination have been reviewed. [4] A wide variety of vanadium complexes have been synthesized and used as functional models for V-haloperoxidases in order to have a better understanding of the mechanism of action of such enzymes, and these complexes are effective catalyst precursors in various oxidation reactions such as epoxidation of alkenes, oxidation of sulfides, alkanes, arenes and alcohols, as well as in oxidative bromination reactions in the presence of hydrogen peroxide [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] or alkyl hydroperoxides. [26] Inspired by the mechanism of action of V Br PO, a biphasic procedure for bromination reactions was proposed in 1994.…”

Vanadium(V) and Molybdenum(VI) Complexes Containing ONO Tridentate Schiff Bases and Their Application as Catalysts for Oxidative Bromination of Phenols

“…Both ligands exhibit one peak at ca . 1.0 V due to oxidation of the hydrazine‐based ligand . The cyclic voltammograms’ pattern of dioxidomolybdenum(VI) complexes showed only one reductive response in the potential window −0.82 to –0.98 V attributed to the Mo VI → Mo V reduction and is irreversible in nature .…”