Abstract
The full speciation of vanadium(V) complexation systems with glycinehydroxamic acid and three α-aminohydroxamic acids (α-alanine-, α-threonine- and α-lysine-) has been achieved using potentiometric and spectroscopic techniques. Formation constants were calculated in a systematic study at different concentrations and ligand-to-metal molar ratios. In each case, in a neutral medium, two complexes were identified with 1:1 and 1:2 metal-to-ligand ratios, both of which can either be protonated or deprotonated depending on the acidity or basicity of the medium. Structures are proposed based on 51V NMR results. The 1:1 complex, VO 2L ( VO 2 + = dioxovanadium(V) ion and L − = α-aminohydroxamate ligand), has a distorted trigonal bipyramidal structure in neutral medium and it exists as VO 2 HL + in acidic and as VO 2 (OH)L - in basic medium. The 1:2 complex, VO 2 H 2 L 2 + , which is formed in neutral medium, has an octahedral structure and also exists as VO 2 H 3 L 2 2 + and VO 2 HL 2 , in acidic and basic media, respectively. In all cases, only the hydroxamate group appears to be coordinated to the VO 2 + group.
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