A new ligand incorporating a dioxime moiety, (2E,3E)-3- [(2-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}phenyl)imino]butan-2-one oxime, (H 2 Phmdo) (3) has been prepared by reacting 2,3-butanedionemono-{O-[4-(1-methyl-2-oxo-propylideneaminooxy)-2,3-bis-(1-methyl-2-oxo-propylideneaminooxy-methyl)-but-2-enyl]-oxime} (2) with 1,2-phenylenediamine. Mono-, di-and trinuclear copper(II) and/or nickel(II) complexes of H 2 Phmdo were characterized by elemental analyses, magnetic moments, 1 H-n.m.r. and 13 C-n.m.r., i.r. and mass spectral studies. The mononuclear copper(II) and nickel(II) complexes of H 2 Phmdo were found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu (II) or Ni (II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu (II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The data support the proposed structure of H 2 Phmdo and its complexes.