1,2-bis(5,7-bis(trimethylsilyl)tricyclo[2.2.1.02,6]heptaphosphan-3-yl)-1,1,2,2-tetramethyldisilane | 1269471-45-5

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: 1,2-bis(5,7-bis(trimethylsilyl)tricyclo[2.2.1.02,6]heptaphosphan-3-yl)-1,1,2,2-tetramethyldisilane
• CAS: 1269471-45-5
• 化学式: C₁₆H₄₈P₁₄Si₆
• 分子量: 842.703
• InChiKey: CYCOLYDAWYWRPG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  19.11
• 重原子数：
  36.0
• 可旋转键数：
  7.0
• 环数：
  8.0
• 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：

  1,2-二氯四甲基二硅烷 、 以 甲苯 为溶剂， 以25%的产率得到1,2-bis(5,7-bis(trimethylsilyl)tricyclo[2.2.1.02,6]heptaphosphan-3-yl)-1,1,2,2-tetramethyldisilane
  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