AbstractThe electrochemical oxidation of anodic metal (cobalt, nickel, copper, zinc and cadmium) in an acetonitrile solution of the Schiff‐base ligand 2‐(tosylamino)‐N‐[2‐(tosylamino)benzylidene]aniline (H2L) afforded the homoleptic compounds [ML]. The addition of 1,1‐diphenylphosphanylmethane (dppm), 2,2′‐bipyridine (bipy) or 1,10‐phenanthroline (phen) to the electrolytic phase gave the heteroleptic complexes [NiL(dppm)], [ML(bipy)] and [ML(phen)]. The crystal structures of H2L (1), [NiL] (2), [CuL] (3), [NiL(dppm)] (4), [CoL(phen)] (5), [CuL(bipy)] (6) and [Zn(Lphen)] (7) were determined by X‐ray diffraction. The homoleptic compounds [NiL] and [CuL] are mononuclear with a distorted square planar [MN3O] geometry with the Schiff base acting as a dianionic (NamideNamideNimineOtosyl) tetradentate ligand. Both compounds exhibit an unusual π–π stacking interaction between a six‐membered chelate ring containing the metal and a phenylic ring of the ligand. In the heteroleptic complex [NiL(dppm)], the nickel atom is in a distorted tetrahedral [NiN3P] environment defined by the imine, two amide nitrogen atoms of the L2– dianionic tridentate ligand and one of the phosphorus atoms of the dppm molecule. In the other heteroleptic complexes, [CoL(phen)], [CuL(bipy)] and [ZnL(phen)], the metal atom is in a five‐coordinate environment defined by the imine, two amide nitrogen atoms of the dianionic tridentate ligand and the two bipyridine or phenanthroline nitrogen atoms. The compounds were characterized by microanalysis, IR and UV/Vis (Co, Ni and Cu complexes) spectroscopy, FAB mass spectrometry and 1H NMR ([NiL] and Zn and Cd complexes) and EPR spectroscopy (Cu complexes).