The group 13 dichlorides of formula Ar'MCl2 [Ar' = 8-(dimethylamino)-1-naphthyl (8-(Me2N)C10H6)], M = Al (1), Ga (2), and In (3), have been prepared via the salt elimination reaction of 1 equiv of Ar'Li with MCl3 in toluene solution at -78 degrees C. The reaction of 1 with LiAlH4 in diethyl ether solution at -78 degrees C produced the dihydride [Ar'AlH2](2) (4). The X-ray crystal structures of 1-4 have been determined and show that 1 and 2 are monomeric while 3 and 4 are dimeric in the solid state. The reaction of 1 with RLi in toluene solution at -78 degrees C results in ligand redistribution and formation of Ar'2AlR (R = Me (5), t-Bu (6)). The chloride analogue of 5 and 6, Ar'2AlCl (7), can be prepared directly from the reaction of 2 equiv of Ar'Li with AlCl3 in toluene solution at -78 degrees C. The homoleptic derivative Ar'Al-3 (8) was obtained when 3 equiv of Ar'Li was employed. Crystal data for 1: monoclinic, space group P2(1), a 6.534(1) Angstrom, b = 10.801(1) Angstrom, c = 9.631(2) Angstrom, beta 105.57(2)degrees, V = 654.8(2) Angstrom(3), Z = 2, R = 0.0453. Crystal data for 2: monoclinic, space group P2(1), a = 6.552(2) Angstrom, b = 10.833(2) A, c = 9.601(2) Angstrom, beta = 106.05(2)degrees, V = 653.9(3) Angstrom(3), Z = 2, R = 0.0609. Crystal data for 3: monoclinic, space group P2(1)/c, a = 7.301(2) Angstrom, b = 15.746 Angstrom, c = 10.801(4) Angstrom, beta = 92.37(3)degrees, V = 1257.6(7) Angstrom(3), Z = 2, R = 0.0712. Crystal data for 4: monoclinic, space group P21/c, a = 13.343(2) Angstrom, b = 11.218(2) A, c = 7.505(1) Angstrom, beta = 100.64(1)degrees, V = 1105.0(4) Angstrom(3), Z = 4, R = 0.0560.