源自N,N'-二叔丁基乙二胺的仲胺稳定氢化铝

Secondary Amine Stabilized Aluminum Hydrides Derived from N,N'-Di-tert-butylethylenediamines.

作者信息

Gardiner Michael G., Lawrence Stacey M., Raston Colin L.

机构信息

Department of Chemistry, Monash University, Clayton, Melbourne, Victoria, 3168, Australia, and Faculty of Science and Technology, Griffith University, Nathan, Brisbane, Queensland, 4111, Australia.

出版信息

Inorg Chem. 1996 Feb 28;35(5):1349-1354. doi: 10.1021/ic950978a.

DOI:10.1021/ic950978a

PMID:11666331

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.

摘要

研究了各种氢化铝源对取代的N，N'-二叔丁基乙二胺的金属化作用。HN(t-Bu)CH(t-Bu)CH₂N(H)(t-Bu)形成LiAlH₄的二聚锂螯合加合物[{[HN(t-Bu)CH(t-Bu)CH₂N(H)(t-Bu)]Li(μ-H)₂AlH₂}₂]，即4，它热分解生成四聚锂二氨基氢化铝[{Li[N(t-Bu)CH(t-Bu)CH₂N(t-Bu)]AlH₂}₄]，即5。相同的二胺与AlH₃·NMe₃或AlH₃二乙醚合物反应，生成仲胺稳定的氨基氢化铝物种[{HN(t-Bu)CH(t-Bu)CH₂N(t-Bu)}AlH₂]，即2。类似地，相同的氢化铝源与二胺rac-HN(t-Bu)CH(Me)CH(Me)N(H)(t-Bu)反应，生成[{rac-HN(t-Bu)CH(Me)CH(Me)N(t-Bu)}AlH₂]，即3。化合物2和3对于消除氢形成二氨基氢化铝是稳定的，但在特殊条件下，通过与AlH₃·NMe₃反应，可以转化为富含铝烷的物种[H₂Al{N(t-Bu)CH(t-Bu)CH₂N(t-Bu)}AlH₂]，即6，以及[H₂Al{rac-N(t-Bu)CH(Me)CH(Me)N(t-Bu)}AlH₂]，即7。这三种氢化铝源在这些反应中不同的反应活性使得能够收集到机理信息，并讨论了二胺中不同空间位阻要求对配合物稳定性的影响。3的晶体为单斜晶系，空间群P2(1)/n（编号14），a = 8.910(4) Å，b = 14.809(1) Å，c = 12.239(6) Å，β = 109.76(2)°，V = 1520(1) Å³，Z = 4。4的晶体为正交晶系，空间群Pbca（编号61），a = 15.906(9) Å，b = 24.651(7) Å，c = 9.933(7) Å，V = 3895(3) Å³，Z = 4。6的晶体为单斜晶系，空间群P2(1)/c（编号14），a = 8.392(1) Å，b = 17.513(2) Å，c = 12.959(1) Å，β = 107.098(8)°，V = 1820.4(3) Å³，Z = 4。