The coordination preferences of the tetradentate Schiff base, N,N′-ethylenebis(acetylacetoimine), H₂L, with a variety of group 13 precursors, led to the formation of a series of mono and binuclear products. The reaction of H₂L with AlMe₃ and Me₂GaCl afforded the binuclear complexes, [L{Al(Me)₂}₂] 1 and [H₂L{GaCl(Me)₂}₂], 3, the latter an adduct of the neutral ligand. Treatment of 1 with iodine generated the cationic Al(III) complex, [LAl(thf)₂]I, 2, while the addition of n-BuLi to H₂L, followed by reaction with GaCl₃ and InCl₃ led to an ionic complex [{LGaCl}₂(μLi)]GaCl₄, 4, an In(III) dimer, [LInCl]₂, 5 and monomeric [LInCl(thf)], 6. In contrast, the reaction of [In{N(SiMe₃)₂}₃] with H₂L yielded a homoleptic, air stable, indium complex, [L₃In₂], 7. All products were definitively characterized by X-ray crystallography and their structures confirmed by pertinent spectroscopic techniques.