A wide range of bimetallic aluminum molecules are formed in combinations between Salen Schiff base ligands and either AlR 3 or AlR 2 Cl. They are of the general formulas L(AlR 2 ) 2 and L(AlRCl) 2 with R ) alkyl and L ) Salen( t Bu) ligand with relatively unusual "backbone" connections between the nitrogen atoms, 1,2-cyclohexylene (Salcen( t Bu)), 1,4-butylene (Salben( t Bu)), 1,5-pentylene (Salpten( t Bu)), 1,6-hexylene (Salhen( t Bu)), and 1,4-phenylene (1,4-Salophen( t Bu)). Additionally, previously unknown ligands were employed with the "backbones" 1,4-bis(p-aminobenzyl)benzene (Salmaben( t Bu)), 1-(m-aminobenzoyl)-4-(m-aminobenzyl)benzene (Salmabmaben( t Bu)), and 4,4′-bis(m-aminobenzoyl)diphenylmethane (Salmadmen( t Bu)). The ligands for these compounds were designed to feature two group 13 sites at long and varying distances from one another. The compounds were characterized by mp analyses, IR, and 1 H NMR, and X-ray structures were determined for the examples R,R′-Salcen( t Bu){AlMe 2 } 2 (1), Salben( t Bu){AlMe 2 } 2 (2), 1,4-Salophen( t Bu){GaEt 2 } 2 (7), R,R′-Salcen( t Bu){AlMeCl} 2 (11), Salben( t Bu){AlMeCl} 2 (13), and Salhen( t Bu){AlMeCl} 2 (14).