SiCl4.TMEDA | 18825-07-5

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: SiCl4.TMEDA
• 英文别名: tetra-N-methyl-ethylenediamine; compound with tetrachlorosilane；Tetra-N-methyl-aethylendiamin; Verbindung mit Tetrachlorsilan
• CAS: 18825-07-5
• 化学式: C₆H₁₆N₂*Cl₄Si
• 分子量: 286.104
• InChiKey: QWTFQPKGFHZUDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.49
• 重原子数：
  13.0
• 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：
  6.48
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  四甲基乙二胺 在 四氯化硅 作用下， 以 正戊烷 为溶剂， 反应 1.0h， 以92%的产率得到SiCl4.TMEDA
  参考文献：
  名称：

  Unexpected Disproportionation of Tetramethylethylenediamine-Supported Perchlorodisilane Cl₃SiSiCl₃

  摘要：

  The addition compound Cl3SiSiCl3-TMEDA was formed quantitatively by treatment of Cl3SiSiCl3 with tetramethylethylenediamine (TMEDA) in pentane at room temperature. The crystal structure of Cl3SiSiCl3 center dot TMEDA displays one tetrahedrally and one octahedrally bonded Si atom (monoclinic, P2(1)/n). Si-29 CP/MAS NMR spectroscopy confirms this structure. Density functional theory (DFT) calculations have shown that the structure of the meridional isomer of Cl3SiSiCl3 center dot TMEDA is 6.3 kcal lower in energy than that of facial coordinate species. Dissolving of Cl3SiSiCl3 center dot TMEDA in CH2Cl2 resulted in an immediate reaction by which oligochlorosilanes SinCl2 (n = 4, 6, 8, 10; precipitate) and the Cl--complexed dianions [SinCl2n+2](2-) (n = 6, 8, 10, 12; CH2Cl2 extract) were formed. The constitutions of these compounds were confirmed by MALDI mass spectrometry. Additionally, single crystals of [Me3NCH2CH2NMe2](2)[Si6Cl14] and [Me3NCH2CH2NMe2](2)[Si8Cl18] were obtained from the CH2Cl2 extract. We found that Cl3SiSiCl3 center dot TMEDA reacts with MeCl, forming MeSiCl3 and the products that had been formed in the reaction of Cl3SiSiCl3 center dot TMEDA with CH2Cl2. X-ray structure analysis indicates that the structures of [Me3NCH2CH2NMe2](2)[Si6Cl14] (monoclinic, P2(1)/n) and [Me3NCH2CH2NMe2](2)[Si8Cl18] (monoclinic, P2(1)/n) contain dianions adopting an "inverse sandwich" structure with inverse polarity and [Me3NCH2CH2NMe2](+) as countercations. Single crystals of SiCl4 center dot TMEDA (monoclinic, Cc) could be isolated by thermolysis reaction of Cl3SiSiCl3 center dot TMEDA (50 C) in tetrahydrofuran (THF).

  DOI：

  10.1021/ic301283m