A 51V NMR investigation of the interactions of aqueous vanadate with hydroxylamine

The aqueous reactions of hydroxylamine and N-methylhydroxylamine with vanadate have been studied. Ligand, vanadium, and proton stoichiometries of the products have been obtained as have their formation constants. At lower ligand concentrations the predominant complex contains a single hydroxamido ligand and this has been assigned a five-coordinate, tetrahedral-like structure where the hydroxamido group is coordinated in a side-on fashion. Four bishydroxamido products were observed. These four complexes consisted of two distinct groups of two isomeric complexes each and have been assigned six-coordinate (tetrahedral-like) and seven-coordinate (trigonal bipyramidal-like) geometries. For the N-methylhydroxamido ligand, 10 bisligand products in 2 groups of 5 isomers each were observed. The additional products over the hydroxylamine situation arise from the relative orientations of the ligand methyl groups. For both ligands, the monoligand products carried a single negative charge and did not have a pKa, within the range of about 6–10. The bisligand products did not carry a charge under neutral conditions. The tetrahedral bisligand products could be protonated under acidic conditions (pKa ~ 6.6) but could not be deprotonated. In contrast, the trigonal bipyramidal products were not protonated under acidic conditions but could give up a proton under basic conditions (pKa ~ 7.4) to form anionic complexes. The relative orientations of the ligands and also the number of methyl groups and their relative orientations in the complex have a significant influence on the 51V chemical shifts. One additional complex was observed to form and was assigned to an ester-like product formed by reaction at the hydroxyl group. Keywords: vanadate, complexes, hydroxylamine, methylhydroxylamine, peroxovanadate.