Reactions of AlCl3 with 1 equiv of LiC4H2N(CH2NMe2)2-2,5 or 2 equiv of LiC4H3N(CH2NMe2)-2 in diethyl ether at 78 C afforded AlCl2C4H2N(CH2NMe2)2-2,5 (1) and AlClC4H3N(CH2NMe2)-2 (2), respectively. Alkylation of 1 with MeLi in diethyl ether generates the aluminum dimethyl complex 3. Compound 2 is thermally unstable and was converted to uncharacterized product in CHCl3 within 2 days at 80 C. Compounds 1, 2, and 3 were characterized by NMR spectroscopy and X-ray structure determination.