title: 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.
authors.affiliation: Department of Chemistry, Indian Institute of Engineering Science and Technology , Shibpur, Howrah 711 103, India.
authors.forename: Chandrima
authors.initials: C
authors.lastname: Das
authors.forename: Piyali
authors.initials: P
authors.lastname: Adak
authors.forename: Satyajit
authors.initials: S
authors.lastname: Mondal
authors.forename: Ryo
authors.initials: R
authors.lastname: Sekiya
authors.forename: Reiko
authors.initials: R
authors.lastname: Kuroda
authors.forename: Serge I
authors.initials: SI
authors.lastname: Gorelsky
authors.forename: Shyamal Kumar
authors.initials: SK
authors.lastname: Chattopadhyay
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism; D010544:Peroxidases / Q000737:chemistry* / Q000378:metabolism; D011789:Quantum Theory; D014638:Vanadates / Q000737:chemistry* / Q000378:metabolism; D014639:Vanadium / Q000737:chemistry* / Q000378:metabolism
chemical_list: D009942:Organometallic Compounds; D014639:Vanadium; D014638:Vanadates; D010544:Peroxidases; C026195:bromide peroxidase