The reactions of a pair each of monosubstituted anilines PhNHR¹ and disubstituted 1,2-diaminobenzenes C₆H₄(NHR¹)₂-1,2 (R¹ = SiMe₃ = R, or R¹ = CH₂Bu^t = R′) with 1 or 2 equivalents of trimethylalane have been investigated. The trimethylsilyl derivatives were more reactive than the neopentyl analogues. The following crystalline compounds were obtained at ambient temperature or (1) gentle heating: trans-[AlMe₂(μ-NRPh)]₂1, [AlMe₃{NH(R′)Ph}] 2, [(AlMe₂)₂{μ-(NR)₂C₆H₄-1,2}] 4, [(AlMe₂){μ-(NR′)₂C₆H₄-1,2}] 5, [(AlMe){N(R)C₆H₄NR-μ-1,2}]₂6 and [AlMe₂{N(R′(C₆H₄N(H)R′}] 7, while prolonged heating was required in order to obtain [AlMe₂(μ-NR′Ph)]₂3 and [(AlMe{N(R′)C₆H₄NR′-μ-1,2}]₂8. The amine adducts 2 and 7, were identified as intermediates to 3 and 8, respectively. Treatment of C₆H₄(NHR′)₂-1,2 with successively 2 LiBuⁿ and 2 AlCl₃ afforded [AlCl{N(R′)C₆H₄NR′-µ-1,2}]₂9. The diamine adduct [C₆H₄{N(H)R′(AlMe₃)}₂-1,3] 10 was obtained from C₆H₄(NHR′)₂-1,3 and 2 AlMe₃; while the same diamine with successively 2 LiBuⁿ, 2 AlClMe₂ and 2 tmen yielded a compound tentatively formulated as [C₆H₄{N(R′)AlMe₂(tmen)}₂-1,3] 11. The X-ray structures of 1–7, 9 and 10 are presented.