The reactions of Cu 2+, Co 2+, and Ni 2+ ions with N-phenyl-N-2-hydroxybenzyl- and N-phenyl-N-2-hydroxynaphthylmethyleneamine derivatives (HL n, n = 1-8) produced from the derivatives of aniline and aromatic -hydroxyaldehydes are studied. Among the ions studied, only Cu 2+ forms stable complexes Cu(L n) 2 · 2H 2O. The structures of the synthesized compounds are studied by IR, UV, and EPR spectroscopies and differential thermal analysis. The magnetic moments of the Cu(L n) 2 · 2H 2O complexes are very small and range within 0.43-1.19 μ B, depending on the ligand structure, which indicates a strong antiferromagnetic interaction between the Cu 2+ ions. The temperature dependence of the magnetic susceptibility measured for the Cu(L 3) 2 ·2H 2O complex (where HL 3 is N-4-methoxyphenyl-N-2- hydroxybenzylamine) is closest to the theoretical curve calculated for the binuclear Cu(II) complexes connected by the intermolecular exchange interaction. The Cu(II) complexes with HL n are shown to undergo oxidative dehydrogenation to form the corresponding metal salicyl-aldiminates. This reaction can occur on heating in the absence of oxygen and is accompanied by the Cu 2+ → Cu + transition.