Syntheses and Structures of Intramolecularly Stabilized Organoaluminium Compounds

The reaction of LiAr (Ar = 2‐[(dimethylamino)methyl]phenyl) with AlCl3, MeAlCl2, and Me2AlCl in a 1:1 ratio yields the corresponding organoaluminium compounds ArAlCl2, ArAl(Cl)Me, and ArAlMe2 (1–3). The alanes Ar2AlCl and Ar2AlMe (4 and 5) were synthesized from AlCl3 and MeAlCl2 with two equivalents of LiAr. The products ArAl(Cl)R [R = tBu, C(SiMe3)3] 6 and 7 are formed by the reaction of LiR with 1. The Lewis acid 1 adds the bases iPrNH2 and THF to yield the adducts 1 · iPrNH2 and 1 · THF. The structures of the products were deduced from the 1H‐, 13C‐, and 27Al‐NMR spectra and were confirmed by X‐ray structural determinations of 5 and 1 · iPrNH2.