Some ternary complexes of oxovanadium(IV) with acetylacetone and N-(2-pyridyl)-N′-(salicylidene)hydrazine and its derivatives

The reactions of one equivalent each of [VO(acac)2] and N-(2-pyridyl)-N′-(5-R-salicylidene)hydrazines (HphsalR) (derived from 2-hydrazinopyridine and 5-substituted salicylaldehydes) in boiling acetonitrile under aerobic conditions provide ternary complexes of oxovanadium(IV) having the general formula [VO(phsalR)(acac)]. The complexes have been characterized by analytical, magnetic and spectroscopic measurements. The structures of two representative complexes have been determined by X-ray crystallography. In each structure, the metal centre is in a distorted octahedral N2O4 coordination sphere. The tridentate phsalR− coordinates the metal ion via the pyridine-N, the imine-N and the phenolate-O atoms in a meridional fashion. The remaining three coordinations sites are occupied by the bidentate O,O-donor acetylacetonate (acac−) and the oxo group. In the crystal lattice, the molecules of each of the two complexes assemble to form one-dimensional supramolecular structure via intermolecular N–H⋯OV hydrogen bond interaction. Electronic spectra collected using dimethylsulfoxide solutions of the complexes display a weak absorption within 643–720 nm due to d–d transition and some strong absorptions in the range 510–262 nm due to ligand-to-metal charge transfer and ligand centred transitions. The room temperature (298 K) effective magnetic moments of the complexes in the solid state are consistent with an S = 1/2 ground state of the metal ion in each complex. All the complexes display axial EPR spectra with well-resolved 51V hyperfine structure characteristic of an axially compressed octahedral coordination geometry around the metal centre.

Synthesis and physical properties of a series of ternary oxovanadium(IV) complexes having the formula [VO(phsalR)(acac)] (HphsalR = N-(2-pyridyl)-N′-(5-R-salicylidene)hydrazine and Hacac = acetylacetone) have been described. X-ray structures reveal distorted octahedral N2O4 coordination sphere around the metal centre and intermolecular N–H⋯OV hydrogen bond assisted self-assembly to one-dimensional ordering in the crystal lattice.Figure optionsDownload as PowerPoint slide