| 1269471-54-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• CAS: 1269471-54-6
• 化学式: C₂₁H₆₃P₇Si₉
• 分子量: 785.317
• InChiKey: ALWRAWXNAJFMEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.86
• 重原子数：
  37.0
• 可旋转键数：
  9.0
• 环数：
  4.0
• 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：

  tris(trimethylsilyl)heptaphosphine 、 氯三(三甲基甲硅烷基)硅烷 以 乙二醇二甲醚 为溶剂， 反应 2.0h， 以90%的产率得到
  参考文献：
  名称：

  Derivatization of Tris(trimethylsilyl)heptaphosphane

  摘要：

  Through SiP bond cleavage, the reaction of P(7)(SiMe(3))(3) with one equivalent of KO(t)Bu or LiO(t)Bu afforded different isomers of the heptaphosphanide anion [P(7)(SiMe(3))(2)](-). With LiO(t)Bu, concomitant inversion at an equatorial (silylated) phosphorus atom occurred and the C(s) symmetric isomer characterized by a mirror plane formed. With KO(t)Bu, inversion did not occur and the resulting asymmetric anion with C(1) symmetry formed. With NaO(t)Bu, a mixture of both isomers was obtained. The symmetries and structures of the anions were elucidated with (31)P{(1)H} and (29)Si{(1)H} NMR spectroscopy, and relative stabilities were calculated employing the B3LYP/6-31+G* method.The reaction of KP(7)(SiMe(3))(2) or LiP(7)(SiMe(3))(2) with 1,2-dichlorotetramethyldisilane led to (SiMe(3))(2)P(7)-SiMe(2)SiMe(2)P(7)(SiMe(3))(2), a molecule composed of two P(7)-cages connected by a disilane bridge. It can also be obtained through silyl exchange using P(7)(SiMe(3))(3) and ClMe(2)SiSiMe(2)Cl. The compound was characterized with (31)P and (29)Si-NMR spectroscopy and elemental analysis. Treatment of P(7)(SiMe(3))(3) with HypCl (Hyp = hypersilyl = Si(SiMe(3))(3)) in DME led to the quantitative formation of Hyp(2)P(7)SiMe(3). Single crystal X-ray diffraction as well as (31)P and (29)Si-NMR spectroscopy proves the presence of a heteroleptically substituted heptaphosphane cage.Quantum chemical HF and B3LYP/6-31G* calculations of equilibrium structures for the two possible isomers of P(7)(SiMe(3))(3) (sym and asym) reveal that asym is destabilized by about 30-40 kJ mol(-1), which explains why its formation could not be observed. The phosphorus inversion barrier for the sym -> asym transition is calculated as 60-70 kJ mol(-1). (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.09.040