The reaction of the aluminum triamide [{HN(t-Bu)CH2CH2N-t-Bu)Al(N(t-Bu)CH2)(2)] (1) with n-BuLi in hexane and diethyl ether gives the monomeric solvent-free lithium aluminum tetraamide [Li(N(t-Bu)CH2CH2N-t-Bu)(2)Al] (2), and the diethyl ether adduct [Et2O . Li(N(t-Bu)CH2CH2N-t-Bu)(2)Al] (3), respectively. The reaction of the diethyl ether adduct 3 with 2 equiv of the chelating nitrogen Lewis bases TMEDA (=N,N,N’,N’-tetramethylethylenediamine) and t-Bu(2)DAB (=N,N’-di-tert-butyl-1,4-diazabutadiene) in diethyl ether affords the ionic complex [Li(TMEDA)(2)][Al{[N(t-Bu)CH2](2)}(2)] (4) and a mixture of;the paramagnetic species [Li(t-BuDAB)(2)] and [Al ([N(t-Bu)CH2](2)}(2)], which cocrystallize 5, respectively. The reaction of the diethyl ether adduct 3 with 0.5 equiv of HgCl2 yields the neutral paramagnetic species [AI([N(t-Bu)CH2](2)}(2)] (6). Crystals of 2 are triclinic, of space group (No. 2), with a = 15.894(5) Angstrom, b = 15.473(5) Angstrom, c = 9.975(3) Angstrom, a 93.74(2)degrees, beta = 91.97(2)degrees, gamma = 102.07(3)degrees, and Z = 4. Crystals of 3 are monoclinic, of space group C2/c (No. 15), with a = 15.835(5) Angstrom, b = 12.054(3) Angstrom, c = 16.456(5) Angstrom, beta = 111.56(3)degrees, and Z = 4. Crystals of 4 are orthorhombic, of space group Pbca (No. 61), with a = 19.349(4) Angstrom, b = 22.227(7) Angstrom, c = 19070(3) Angstrom, and Z = 8. Crystals of 5 are orthorhombic, of space group Pmmn (No. 59), with a = 13.874(4) Angstrom, b = 13.473(6) Angstrom, c = 12.717(3) Angstrom, and Z = 2. Crystals of 6 are monoclinic, of space group C2/c (No. 15), with a = 16.721(4) Angstrom, b = 9.454(4) Angstrom, c 16.460(8) Angstrom, beta = 113.27(3), and Z = 4.