Effects of side chain amino nitrogen donor atoms on metal complexation of aminohydroxamic acids: New diaminohydroxamates chelating Ni(ii) more strongly than Fe(iii)

Abstract

Complexes of diaminohydroxamic acids 2,6-diamino-N-hydroxyhexanamide (lysinehydroxamic acid, Lysha), 2,4-diamino-N-hydroxybutanamide (2,4-diaminobutyrohydroxamic acid, Dambha) and 2,3-diamino-N-hydroxypropanamide (2,3-diaminopropionohydroxamic acid, Dampha) with manganese(II), cobalt(II), iron(II), nickel(II), copper(II), zinc(II), iron(III), aluminium(III) and molybdenum(VI) in aqueous solution were studied by pH-potentiometric, UV–visible spectrophotometric and EPR methods. The two latter diaminohydroxamic acids were synthesised as new ligands and characterised. The results were compared to those of a simple α-amino acid derivative, α-alaninehydroxamic acid (α-Alaha) and the effects of the side chain amino group on the co-ordination mode and on the stability of the complexes formed were evaluated. As expected, the side chain amino nitrogen atom of Lysha does not co-ordinate to any of the studied metals but remains free for possible further interactions. The amino groups do not co-ordinate to aluminium(III) or iron(III) at all and the closer the side chain amino group is situated to the α-aminohydroxamic residue the less stable the hydroxamate complex formed in the order of Lysha, Dambha, Dampha, and hydrolytic processes become increasingly dominant. The co-ordination of the side chain amino nitrogen of Dampha and Dambha to nickel(II) and copper(II) was unambiguously observed.