| 156646-58-1

• CAS: 156646-58-1
• 化学式: C₂₈H₆₃Al₇O₇
• 分子量: 700.675
• InChiKey: RZVJJTOIMUANPG-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  以 正己烷 为溶剂， 以2.7%的产率得到
  参考文献：
  名称：

  Tert-Butylaluminum Hydroxides and Oxides: Structural Relationship between Alkylalumoxanes and Alumina Gels

  摘要：

  The hydrolysis of Al((t)Bu)3 in toluene using the hydrated salt Al2(SO4)3.14H2O results in the formation of the dimeric hydroxide [((t)Bu)2Al(mu-OH)]2 (1) and [Al4((t)BU)7(mu3-O)2-OH)] (2) as the major and minor products, respectively. Compound 1 may also be prepared by the addition of water to a refluxing toluene solution of Al((t)Bu)3. Compound 1 is remarkably stable to thermolysis and is converted slowly to a mixture of alumoxane species. Dissolution of compound 1 in MeCN or THF yields the hydrogen-bound trimeric complexes [((t)Bu)2Al(mu-OH)]3.Nmecn (n = 1(3), 2) and [((t)Bu)2Al(mu-OH)]3.2THF, respectively. The large-scale synthesis of alumoxanes from the low temperature thermolysis of the trimeric hydroxide [((t)Bu)2Al(mu-OH)]3 allows for the isolation of the pentaaluminum compound [Al5((t)Bu)7(mu3-O)2(mu-OH)2] (4) and the heptameric alumoxane [((t)Bu)Al(mu3-O)]7 (5). The structure of compound 4 is consistent with the condensation of [((t)Bu)2Al(mu-OH)]3 With [((t)Bu)2Al(mu-OH)]2. Thermolysis of 4 yields an alumina gel. The structural relationship of 4 with respect to the structures reported for non-alkyl alumoxanes and alumina gels is discussed. The low-temperature thermolysis of [((t)Bu)2Al(mu-OH)]3 in pentane yields [((t)Bu)Al(mu3-O)]6 as the major product and allows for the isolation of a possible precursor to the hexamer, the ''basket'' structured [Al6((t)Bu)8(mu3-O)4(mu-OH)2] (6). When it is heated, compound 6 is readily converted into [((t)Bu)Al(mu3-O)]6, with concomitant liberation of isobutane. Reaction of [((t)Bu)2Ga(mu-OH)]3 with Al((t)Bu)3 in toluene yields Ga((t)Bu)3 and the octameric alumoxane [((t)Bu)Al(mu3-O)]8 (7) as the major isolable products. Mass spectrometry indicates the incorporation of low levels of gallium (<8%) into samples of 7 made by this route. A topological relationship for the prediction of the structures of ''closed'', cage alumoxane compounds [((t)Bu)Al(mu3-O)]. is suggested: the stable structures of [((t)Bu)Al(mu3-O)]n will have six four-membered Al2O2 rings and n - 1 six-membered Al3O3 rings. This relationship is discussed with respect to the known structures for main-group clusters with n = 4-12. The molecular structures of compounds 2, 4, 6, and 7 have been determined by X-ray crystallography. Crystal data for 2: monoclinic, P2(1)/c, a = 10.012(6) angstrom, b = 9.426(3) angstrom, c = 39.14(1) angstrom, beta = 92.53(l)-degrees, Z = 4, R = 0.098, R(w) = 0.101. Crystal data for 4: monoclinic, P2(1)/c, a = 17.204(3) angstrom, b = 11.337(2) angstrom, c = 20.143(4) angstrom, beta = 97.84(3)-degrees, Z = 4, R = 0.054, R(w) = 0.055. Crystal data for 6: triclinic, P1BAR, a = 10.343(5) angstrom, b = 11.776(8) angstrom, c = 19.45(1) angstrom, alpha = 100.05(1)-degrees, beta = 94.64(1)-degrees, gamma = 107.15(1)-degrees, Z = 2, R = 0.102, R(w) = 0.122. Crystal data for 7: monoclinic, C2/c, a = 19.831(7) angstrom, b = 12.980(7) angstrom, c = 19.753(5) angstrom, beta = 103.20(4)-degrees, Z = 8, R = 0.047, R(w) = 0.0053.

  DOI：

  10.1021/om00020a011