The reactions of the diaminebis(aryloxido) ligand precursors [Me2NCH2CH2N(CH2-4-R-C6H3OH)2] [R = C(CH3)2CH2C(CH3)3, H22L11; R = CH3, H22L22] with MgnBu2, ZnEt2 and AlEt3 create complexes of general formula [M2(μ-L-κ4O,N,N,O)2] (M = Mg, 1a for L1 and 1b for L2; M = Zn, 2a for L1 and 2b for L2) and [Al2(μ-L-κ3O,N,N,O)2Et2] (3 for L1) in good yields. Compounds 1a–3 were characterized by NMR spectroscopy and ESI-MS experiments. The definitive molecular structure of 1b·CH2Cl2, 2a·H2O, 2b·CH2Cl2 and 3 was provided by a single-crystal analysis and revealed their dimeric nature with an M2O2 planar core. The L1 and L2 ligands coordinate as the dianions in a tetradentate/bridging manner in 1b, 2a, 2b and in a tridentate/bridging mode in 3. The NMR spectra showed that the solid state of these compounds is essentially retained in solution.