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
= CH2But
= 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.