Herein is presented the synthesis and characterization of the alkylaluminum lithium amides of the general formula [R(2)AlNLi(THF)(n)R’](2) (where R, R’=Me, (t)Bu(n=1) (1); (t)Bu, Ph(n=1) (2); SiMe(3), Ph(n=2) (3)). When the relatively bulky groups Mes or Dipp (Mes=2,4,6-trimethylphenyl, Dipp=2,6-diisopropylphenyl) are used, the unusual adducts Me(2)((t)Bu)Al-NHLi(THF)(3)Dipp (4) and Mes(2)(Me)Al-NLi(THF)(2)(SiMe(3))(2) (6) and aluminate [(t)Bu(2)((t)Bu)AlNHDipp](-)[Li(THF)(4)](+) (5) result. One other type of aluminate of relevance to this study is the related complexes [Mes(2)al(NH(t)Bu)(2)]li(THF)(n) (where n=1 (7) and 2(8)). Crystal data for 1 : triclinnic, , a=9.018(2) Angstrom, b=9.056(1) Angstrom, c=9.429(2) Angstrom, alpha=109.23(1)degrees, beta=90.29(1)degrees, gamma=102.82(1)degrees, V=706.4(2) Angstrom(3), Z=2, with 1070 reflections with F>6.0 sigma(F), R=0.0697. Crystal data for 2 : monoclinic, P2(1)/n, a=10.584(1) Angstrom, b=14.469(1) Angstrom, c=13.599(1) Angstrom, beta=94.40(1)degrees, V=2076.4(3) Angstrom(3), Z=4, with 1323 reflections with F>6.0 sigma(F), R=0.0741. Crystal data for 4 : monoclinic, Cc, a=18.215(3) Angstrom, b=10.498(1) Angstrom c=18.217(4) Angstrom, beta=106.12-(1)degrees, V=3347(1) Angstrom(3), Z=4, with 1423 reflections with F>4.0 sigma(F), R=0.065. Crystal data for 5 : monoclinic, P2(1)/n, a=10.262(1) Angstrom, b=26.899(5) Angstrom, c=16.687(2) Angstrom, beta=99.27(1)degrees, V=4540(1) Angstrom(3), Z=4, with 1958 reflections with F>6.0 sigma(F), R=0.0755. Crystal data for 7 : monoclinic, P2(1)/n, a=17.005(2) Angstrom, b=10.925(2) Angstrom, c=17.138(2) Angstrom, beta=95.52(1)degrees, V=3169.2(8) Angstrom(3), Z=4, with 1361 reflections with F>6.0 sigma(F), R=00.657. Crystal data for 8 : monoclinic, Cc, a=14.28(2) Angstrom, b=19.829(5) Angstrom, c=16.160(7) Angstrom, beta=111.33(1)degrees, V=4264(5) Angstrom(3), Z=8, with 1172 reflections with F>4.0 sigma(F), R=0.0933.