Vanadium plays an important role in biological systems and exhibits a variety of bioactivities. In an effort to uncover the chemistry and biochemistry of vanadium with nitrogen- and oxygen-containing ligands, we report herein the synthesis and spectroscopic characterization of vanadium(IV) complexes with hydrazide ligands. Substituents on these ligands exhibit systematic variations of electronic and steric factors. Elemental and spectral data indicate the presence of a dimeric unit with two vanadium(IV) ions coordinated with two hydrazide ligands along with two H(2)O molecules. The stability studies of these complexes over time in coordinating solvent, DMSO, indicates binding of the solvent molecules to give [V2O2L2(H2O)2(DMSO)2]2+ (L=hydrazide ligand) and then conversion of it to a monomeric intermediate species, [VOL(DMSO)3]1+. Hydrazide ligands are inactive against urease, whereas vanadium(IV) complexes of these ligands show significant inhibitory potential against this enzyme and are found to be non-competitive inhibitors. These complexes also show low phytotoxicity indicating their usefulness for soil ureases. Structure-activity relationship studies indicate that the steric and/or electronic effects that may change the geometry of the complexes play an important role in their inhibitory potential and phytotoxicity.

The synthesis, spectroscopic, enzyme-inhibition, and free-radical-scavenging properties of a series of vanadium(IV) complexes, compounds 1-10, were investigated. These complexes exhibit a dimeric structure with hydrazide ligands coordinated in a bidentate fashion. All complexes are stable in the solid state, but exhibit varying degrees of stability in solution. In coordinating solvent such as DMSO, stepwise binding of two solvent molecules at the 6th positions trans to the V double bond O bond of the dimeric unit is observed. The dimeric compounds are converted to monomeric species in which both solvent molecules and the hydrazide ligands are coordinated to the V(IV) center. The free hydrazide ligands 11-20 were inactive against alpha-glucosidase, but the V(IV) complexes showed varying degrees of inhibition, depending on the type of ligand. The DPPH-radical-scavenging activities of 1-20 were determined, which indicated that steric and/or electronic effects responsible for changes in geometry play important roles in terms of antioxidant potential.