title: Secondary Amine Stabilized Aluminum Hydrides Derived from N,N'-Di-tert-butylethylenediamines.
abstract: The metalation of substituted N,N'-di-tert-butylethylenediamines by various aluminum hydride sources has been investigated. HN(t-Bu)CH(t-Bu)CH(2)N(H)(t-Bu) forms a dimeric lithium chelated adduct of LiAlH(4), [{[HN(t-Bu)CH(t-Bu)CH(2)N(H)(t-Bu)]Li(&mgr;-H)(2)AlH(2)}(2)], 4, which thermally decomposes to yield the tetrameric lithium diamidoaluminum hydride [{Li[N(t-Bu)CH(t-Bu)CH(2)N(t-Bu)]AlH(2)}(4)], 5. The same diamine reacts with AlH(3).NMe(3) or AlH(3) diethyl etherate to give the secondary amine stabilized amidoaluminum hydride species [{HN(t-Bu)CH(t-Bu)CH(2)N(t-Bu)}AlH(2)], 2. Similarly, the same aluminum hydride sources react with the diamine rac-HN(t-Bu)CH(Me)CH(Me)N(H)(t-Bu) to yield [{rac-HN(t-Bu)CH(Me)CH(Me)N(t-Bu)}AlH(2)], 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, [H(2)Al{N(t-Bu)CH(t-Bu)CH(2)N(t-Bu)}AlH(2)],6, and [H(2)Al{rac-N(t-Bu)CH(Me)CH(Me)N(t-Bu)}AlH(2)], 7, by reaction with AlH(3).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 3are monoclinic, space group P2(1)/n (No. 14), with a = 8.910(4), b = 14.809(1), and c = 12.239(6) Å, beta = 109.76(2) degrees, V = 1520(1) Å(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) Å, V = 3895(3) Å(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) Å, beta = 107.098(8) degrees, V = 1820.4(3) Å(3), and Z = 4.
authors.affiliation: Department of Chemistry, Monash University, Clayton, Melbourne, Victoria, 3168, Australia, and Faculty of Science and Technology, Griffith University, Nathan, Brisbane, Queensland, 4111, Australia.
authors.forename: Michael G.
authors.initials: MG
authors.lastname: Gardiner
authors.forename: Stacey M.
authors.initials: SM
authors.lastname: Lawrence
authors.forename: Colin L.
authors.initials: CL
authors.lastname: Raston