tetrakis(triisopropylsilyl)disilene | 158634-75-4

• 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
• 英文名称: tetrakis(triisopropylsilyl)disilene
• 英文别名: [bis[tri(propan-2-yl)silyl]silylidene-tri(propan-2-yl)silylsilyl]-tri(propan-2-yl)silane
• CAS: 158634-75-4
• 化学式: C₃₆H₈₄Si₆
• 分子量: 685.576
• InChiKey: ZITAWHVIRSVCOE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.08
• 重原子数：
  42
• 可旋转键数：
  16
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tetrakis(triisopropylsilyl)disilene 在 四氯化碳 作用下， 以 正己烷 为溶剂， 以70%的产率得到Chloro-[chloro-bis[tri(propan-2-yl)silyl]silyl]-bis[tri(propan-2-yl)silyl]silane
  参考文献：
  名称：

  A Mechanistic Study of Reactions of Stable Disilenes with Haloalkanes

  摘要：

  Mechanisms of the reactions of three tetrakis(trialkylsilyl)disilenes and a tetraaryldisilene with various haloalkanes such as carbon tetrachloride, chloroform, dichloromethane, which gave the corresponding 1-alkyl-2-chlorodisilanes and/or 1,2-dichlorodisilanes, were investigated in detail. As evidenced by an ESR observation of an intermediate radical, these reactions were quite unusual, farming neutral radical pairs from two closed shell molecules at the first step; no similar reactions have been observed between alkenes and haloalkanes. Low oxidation potentials of these disilenes, large negative activation entropies, and solvent effects for the rates are in good accord with the direct halogen abstraction of disilenes from haloalkanes instead of single-electron transfer at the rate-determining first step. The structure-reactivity relationship of the reactions and the Hammond postulate suggest that the transition state structures for the first step are similar to those for the halogen abstraction by silyl radicals, but more product-like.

  DOI：

  10.1021/ja002798s
• 作为产物：
  描述：

  Bis(triisopropylsilyl)dibromsilan 在 lithium dihydronaphthylide radical 作用下， 以 四氢呋喃 为溶剂， 以11%的产率得到tetrakis(triisopropylsilyl)disilene
  参考文献：
  名称：

  Kira, Mitsuo; Maruyama, Toyotaro; Kabuto, Chizuko, Angewandte Chemie, 1994, vol. 106, # 14, p. 1575 - 1577

  摘要：

  DOI：

文献信息

• Stable cyclic and acyclic persilyldisilenes
  作者：Mitsuo Kira、Takeaki Iwamoto

  DOI：10.1016/s0022-328x(00)00439-3

  日期：2000.10

  we have synthesized are described in detail. Due to the remarkable electronic and steric effects of trialkylsilyl substituents, tetrakis(trialkylsilyl)disilenes (RR′SiSiRR′: R, R′=i-Pr2MeSi (1a), t-BuMe2Si (1b), i-Pr3Si (1c); R=i-Pr2MeSi, R′=t-BuMe2Si (1d)) showed interesting features in the geometry around SiSi bond, electronic spectra, 29Si-NMR resonances of the unsaturated silicon nuclei, E,Z-isomerization

  我们已经详细描述了我们合成的全硅烷基化环状和无环二烯的合成，结构和反应。由于三烷基甲硅烷取代基的显着的电子和空间影响，四（三烷基甲硅烷）二硅烯（RR'SiSiRR'：R，R'=我-Pr 2 MESI（1A），吨-BuMe 2的Si（1B），我- PR 3的Si（1C）; R =我-Pr 2个MESI，R'=吨-BuMe 2的Si（1D））显示在周围SiSi键，电子光谱，几何有趣的特性29不饱和硅核的Si-NMR共振，E，Z异构化，碱金属还原以及与醇，烷基锂，烯烃，炔烃和卤代烷烃的各种双分子反应。作为第一cyclooligosilenes，1-三（吨丁基二）甲硅烷基-2,3,3-三（吨丁基二甲基）环三硅烯（2）和六（吨丁基二甲基硅烷）cyclotetrasilene（3）中典型地通过的还原合成相应的三（三烷基甲硅烷基）甲硅烷基三卤代硅烷，分别在THF中的石墨和在甲苯中的钠。3的光化学转化为相应的双环[1
• Novel 1,2-Dilithiodisilanes Derived from Reduction of Stable Tetrakis(trialkylsilyl)disilenes with Lithium Metal
  作者：Mitsuo Kira、Takeaki Iwamoto、Dongzhu Yin、Toyotaro Maruyama、Hideki Sakurai

  DOI：10.1246/cl.2001.910

  日期：2001.9

  1,2-Dilithiotetrakis(trialkylsilyl)disilanes [(R3Si)2SiLi]2 (R3Si = t-BuMe2Si and i-Pr2MeSi) were prepared as stable off-white powder by the reduction of the corresponding tetrakis(trialkylsilyl)disilenes with lithium in THF. The 1,2-dilithiodisilanes reacted with water, iodomethane, and chlorosilanes to give the corresponding disubstituted products in high yields.

  通过在 THF 中用锂还原相应的四（三烷基甲硅烷基）二硅烯，制备稳定的灰白色粉末形式的 1,2-二锂四（三烷基甲硅烷基）二硅烷 [(R3Si)2SiLi]2（R3Si = t-BuMe2Si 和 i-Pr2MeSi） 。 1,2-二锂二硅烷与水、碘甲烷和氯硅烷反应，以高产率得到相应的二取代产物。