Monomeric aluminum chloride amides with the general formula LAI(CI)NR2 (1, R = Me; 2, R = iPr; 3, R = SiMe3; L = HC[C(Me)N(Ar)](2); Ar = 2,6-iPr(2)C(6)H(3)) were prepared by selected routes. Treatment of LAIBr(2) (4) and LAII(2) with LiNMe2 yielded LAI(Br)NMe2 (5) and LAI(I)NMe2 (6), respectively. The alkylation of 1 and 2 with MeLi gave the corresponding methylated compounds LAI(Me)NR2 (7, R = Me; 8, R = iPr); however, no reaction of 3 with MeLi was observed because of steric hindrance. Subsequent fluorination of 1-3 afforded LAI(F)NR2 (9, R = Me; 10, R = iPr; 11, R = SiMe3)- Compounds 1-11 were characterized by multinuclear NMR, electron impact mass spectrometry, and IR. The constitution of compounds 1-3 was confirmed by single-crystal X-ray diffraction studies.