The metalation of substituted N,N’-di-tert-butylethylenediamines by various aluminum hydride sources has been investigated. HN(t-Bu)CH(t-Bu)CH2N(H)(t-Bu) forms a dimeric lithium chelated adduct of LiAlH4, [{[HN(t-Bu)CH(t-Bu)CH2N(H)(t-Bu)]Li(mu-H)(2)AlH2}(2)], 4, which thermally decomposes to yield the tetrameric lithium diamidoaluminum hydride [{Li[N(t-Bu)CH(t-Bu)CH2N(t-Bu)]AlH2}(4)], 5. The same diamine reacts with AlH3 .-NMe(3) or AlH3 diethyl etherate to give the secondary amine stabilized amidoaluminum hydride species [{HN(t-Bu)CH(t-Bu)CH2N(t-Bu)}AlH2], 2. Similarly, the same aluminum hydride sources react with the diamine rac-HN(t-Bu)CH(Me)CH(Me)N(H)(t-B u) to yield [{rac-HN(t-Bu)CH(Me)CH(Me)N(t-Bu)}AlH2], 3. Compounds 2 and 3 are stable with respect to elimination of hydrogen to form diamidoaluminum hydrides, but can be converted to the alane rich species, [H2Al{N(t-Bu)CH(t-Bu)CH2N(t-Bu)}AlH2], 6, and [H2Al{rac-N(t-Bu)CH(Me)CH(Me)N(t-Bu)}AlH2], 7, by reaction with AlH3 . NMe(3) under special conditions. The varying reactivity of the three aluminum hydride sources in these reactions has enabled mechanistic information to be gathered, and the effect of the different steric requirements in the diamines on the stability of the complexes is discussed. Crystals of 3 are monoclinic, space group P2(1)/n (No. 14), with a = 8.910(4), b = 14.809(1), and c = 12.239(6) Angstrom, beta = 109.76(2)degrees, V = 1520(1) Angstrom(3), and Z = 4. Crystals of 4 are orthorhombic, space group Pbca (No. 61), with a = 15.906(9), b = 24.651(7), and c = 9.933(7) Angstrom, V = 3895(3) Angstrom(3), and Z = 4. Crystals of 6 are monoclinic, space group P2(1)/c (No. 14), with a = 8.392(1), b = 17.513(2), and c = 12.959(1) Angstrom, beta = 107.098(8)degrees, V = 1820.4(3) Angstrom(3), and Z = 4.