| 135525-12-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• CAS: 135525-12-1
• 化学式: AlCl₄*C₉H₂₅PSi₂*H
• 分子量: 390.244
• InChiKey: COEXTJPCWTZPJN-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  6.34
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  ((bis(trimethylsilyl)methyl)dimethyl-l5-phosphaneyl)aluminum(IV) chloride 以 盐酸 为溶剂， 以95%的产率得到
  参考文献：
  名称：

  (Phosphinomethyl)aluminum compounds: the role of coligands and x-ray structure determinations of the heterocycles (TMEDA)LiClAlMe2C(SiMe3)2PMe2 and (Me)(Cl)AlC(SiMe3)2PMe2SiMe2C(SiMe3)PMe2

  摘要：

  From the 1:1 reaction of R2AlCl (a, R = Cl; b, R = Me) with {Li[C(SiMe3)2(PMe2)]}2, six-membered heterocycles [R2AlC(SiMe3)2(PMe2)]2 (1a,b) are obtained. The 1:2 reaction for R = Cl involves a facile methyl migration from the silicon to aluminum and leads to the novel heterocycle (Me)(Cl)Al activated C-(SiMe3)2PMe2SiMe2C(SiMe3)PMe2 (2), exhibiting a number of unusual structural features, as shown by the X-ray structure determination of 2, which crystallizes from pentane (colorless crystals, triclinic, space group P1, a = 9.161 (1), b = 15.280 (2), and c = 11.832 (1) angstrom, alpha = 109.62 (1), beta = 74.57 (1), and gamma = 98.39 (1)-degrees, V = 1500.9 angstrom 3, Z = 2, R = 0.035 for 283 refined parameters and 4841 observables). A formal [3 + 2] cycloaddition is observed in the same 1:1 reaction in the presence of tetramethylethylenediamine (TMEDA) to give five-membered heterocycles (TMEDA)L activated iClAlR2C(SiMe3)2PMe2 (3a,b), incorporating five different elements within the ring. 3b crystallizes from pentane (colorless crystals, monoclinic, space group P2(1)/n, a = 8.915 (1), b = 18.887 (2), and c = 16.558 (2) angstrom, alpha = 90.0 (1), beta = 92.52 (1), gamma = 90.0 (1)-degrees, V = 2785.3 angstrom 3, Z = 4, R = 0.064 for 268 refined parameters and 3830 observables). An X-ray structure determination shows the ambidentate phosphinomethanide ligand to be bound to the lithium atom via phosphorus and to the aluminum atom via carbon. 3b thermally is converted to 1b by loss of TMEDA, whereas 3a is stable to thermolysis. In the presence of tetrahydrofuran (THF), the 1:1 reaction for R = Me gives rise to Me2(THF)Al[C(SiMe3)2(PMe2)] (4), which is also obtained from 3b and THF. As a byproduct, due to some traces of HCl, in the 1:1 reaction (R = Cl) the ylide complex Cl3AlC(SiMe3)2PMe2H (5) is identified spectroscopically and eventually can be isolated. 5 either is converted by further addition of HCl to [HC(SiMe3)2PMe2H][AlCl4] (6) or rearranges to its tautomer Cl3AlPMe2C(SiMe3)2H (7), thus constituting a novel example for an ylide half-arrow-right-over-half-arrow-left phosphane diadic relationship. 7 is also obtained directly from AlCl3 and HC(SiMe3)2(PMe2).

  DOI：

  10.1021/om00054a064