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
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Abstract
A vanadium(V) complex with the formula
[Et<sub>3</sub>NH][V<sup>V</sup>O<sub>2</sub>(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 B<sub>6</sub>), 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 O<sub>4</sub>N 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 H<sub>2</sub>O<sub>2</sub> as the oxidizing agent, with model substrate phenol
red, and the vanadium complex as a catalyst show a remarkably high
value of <i>k</i><sub>cat</sub> equal to 26340 h<sup>–1</sup>. The vanadium compound also efficiently catalyzes bromination of
phenol and salicylaldehyde as well as oxidation of benzene to phenol
by H<sub>2</sub>O<sub>2</sub>