Synthesis, Characterization, and Reaction of Aluminum Halide Amides Supported by a Bulky β-Diketiminato Ligand

Monomeric aluminum chloride amides with the general formula LAI(Cl)NR 2 (1, R = Me; 2, R = iPr; 3, R = SiMe 3 ; 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 LiNMe 2 yielded LAI(Br)NMe 2 (5) and LAI(I)NMe 2 (6), respectively. The alkylation of 1 and 2 with MeLi gave the corresponding methylated compounds LAI(Me)NR 2 (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)NR 2 (9, R = Me; 10, R = iPr; 11, R = SiMe 3 ). 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.