heptamethyltrisilane | 812-28-2

• 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: heptamethyltrisilane
• 英文别名: 1H-Heptamethyltrisilan；1,1,1,2,2,3,3-Heptamethyltrisilane；dimethylsilyl-dimethyl-trimethylsilylsilane
• CAS: 812-28-2
• 化学式: C₇H₂₂Si₃
• 分子量: 190.508
• InChiKey: YNNGBLKAOSDCHG-UHFFFAOYSA-N

物化性质

• 沸点：
  61 °C(Press: 22 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  10
• 可旋转键数：
  2
• 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：

  heptamethyltrisilane 生成 Heptamethyltrisilane
  参考文献：
  名称：

  Ballestri Marco, Chatgilialoglu Chryssostomos, Guerra Maurizio, Guerrini +, J. Chem. Soc. Perkin Trans. 2, (1993) N 3, S 421-425

  摘要：

  DOI：
• 作为产物：
  描述：

  1-chloroheptamethyltrisilane 在 lithium aluminium tetrahydride 作用下， 生成 heptamethyltrisilane
  参考文献：
  名称：

  Hassler, K.; Bauer, G., Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 1987, vol. 43, # 11, p. 1325 - 1330

  摘要：

  DOI：

文献信息

• Insertion reaction of dimethylsilylene into Si—H and Si—OR bonds
  作者：Taiyin Yang Gu、William P. Weber

  DOI：10.1016/s0022-328x(00)93384-9

  日期：1980.8

  Dimeyhtylsilylene generated by photolysis of dodecamethylcyclohexasilane inserts sequentially into Si—H and Si—OR bonds of monosilanes to give high yields of the corresponding unsymmetrical di-, tri- and tetrasilanes.

  通过十二甲基甲基环己硅烷的光解反应生成的二甲基乙炔基甲硅烷基依次插入到甲硅烷的Si-H和Si-OR键中，从而得到相应的不对称二，三和四硅烷高收率。
• Synthesis, structure, and reactivity of hydridobis(silylene)ruthenium(IV)-xantsil complexes (xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)) — A stabilized form of key intermediates in the catalytic oligomerization–deoligomerization of hydrosilanes
  作者：Masaaki Okazaki、Jim Josephus Gabrillo Minglana、Nobukazu Yamahira、Hiromi Tobita、Hiroshi Ogino

  DOI：10.1139/v03-151

  日期：2003.11.1

  Ruκ²(Si,Si)-xantsil}(CO)(η⁶-C₆H₅CH₃) (1) was found to be a catalyst for oligomerization–deoligomerization of HSiMe₂SiMe₃ to give H(SiMe₂)_nMe (n = 1–8 at 90 °C for 2 days). Treatment of 1 with HSiMe₂SiMe₂OR (R = Me, t-Bu) led to quantitative formation of Ruκ³(O,Si,Si)-xantsil}(CO)(H)(SiMe₂•••O(R)•••SiMe₂)} (R = Me (2a), t-Bu (2b)), which also worked as a catalyst for oligomerization–deoligomerization of HSiMe₂SiMe₃. Based on these experimental results, a mechanism involving silyl(silylene) intermediates was proposed for the oligomerization–deoligomerization of HSiMe₂SiMe₃. Complex 2a reacted with MeOH in toluene-d₈ to give Ruκ²(Si,Si)-xantsil}(CO)(η⁶-toluene-d₈) and Me₂Si(OMe)₂ with evolution of H₂. Under a CO atmosphere, 2a was smoothly converted to its CO adduct Ruκ²(Si,Si)-xantsil}(CO)₂(H)(SiMe₂•••O(Me)•••SiMe₂)} (3).Key words: silylene complex, ruthenium, polysilane, dehydrogenative coupling, oligomerization.

  已发现 Ruκ²(Si,Si)-xantsil}(CO)(η⁶-C₆H₅CH₃) (1) 是 HSiMe₂SiMe₃ 的寡聚-去聚合催化剂，在90°C处理2天后生成 H(SiMe₂)_nMe (n = 1–8)。将1与HSiMe₂SiMe₂OR (R = Me, t-Bu) 反应，可定量生成 Ruκ³(O,Si,Si)-xantsil}(CO)(H)(SiMe₂•••O(R)•••SiMe₂)} (R = Me (2a), t-Bu (2b))，也可作为 HSiMe₂SiMe₃ 的寡聚-去聚合催化剂。基于这些实验结果，提出了涉及硅烷(硅烯)中间体的寡聚-去聚合机理。在甲苯-d₈中，2a 与 MeOH 反应生成 Ruκ²(Si,Si)-xantsil}(CO)(η⁶-甲苯-d₈) 和 Me₂Si(OMe)₂，伴随释放 H₂。在 CO 气氛下，2a 顺利转化为其 CO 加合物 Ruκ²(Si,Si)-xantsil}(CO)₂(H)(SiMe₂•••O(Me)•••SiMe₂)} (3)。关键词：硅烯配合物、钌、聚硅烷、脱氢偶联、寡聚合。

• Kinetics of insertion reactions of dimethylsilylene
  作者：Iain M. T. Davidson、F. Timothy Lawrence、Naaman A. Ostah

  DOI：10.1039/c39800000859

  日期：——

  Dimethylsilylene, generated by photolysis of dodecamethylcyclohexasilane, inserts into the silicon–hydrogen bond in trimethylsilane and pentamethyldisilane with approximately zero activation energy, while insertion into hydrogen chloride requires an activation energy of 28 kJ mol–1; the results for silicon–hydrogen insertion shed some light on the mechanism of the thermolysis of pentamethyldisilane

  十二甲基环己硅烷的光解反应生成的二甲基甲硅烷基以约零的活化能插入三甲基硅烷和五甲基二硅烷的硅氢键中，而插入氯化氢中则需要28 kJ mol –1的活化能；硅氢插入的结果为五甲基乙硅烷的热分解机理提供了一些启示。
• Coordinatively Unsaturated Ru(II) Species Ru(xantsil)(CO): A New Active Catalyst for Oligomerization/Deoligomerization of HSiMe₂SiMe₃[xantsil=(9,9-Dimethylxanthene-4,5-diyl)bis(dimethylsilyl)]. Isolation of a Stabilized Form of the Silyl(silylene) Intermediates
  作者：Jim Josephus G. Minglana、Masaaki Okazaki、Hiromi Tobita、Hiroshi Ogino

  DOI：10.1246/cl.2002.406

  日期：2002.3

  Ru(xantsil)(CO)(η6-C6H5CH3) (1) was found to be a catalyst for the oligomerization/deoligomerization of HSiMe2SiMe3 to give H(SiMe2)nMe (n=1–8). A possible mechanism involving a silyl(silylene) intermediate was strongly supported by the isolation of its stabilized form, i.e., alkoxy-bridged bis(silylene) complex which was characterized by X-ray crystal structure analysis.

  Ru(xantsil)(CO)(η6-C6H5CH3) (1) 被发现是一种催化剂，用于 HSiMe2SiMe3 的低聚合/解聚反应，生成 H(SiMe2)nMe (n=1–8)。一种涉及硅烯（silylene）中间体的可能机制得到了强有力的支持，因为其稳定形式，即通过醇氧桥连的双（硅烯）络合物被分离出来，并通过X射线晶体结构分析进行了表征。
• Gas-phase photochemical reactions of dodecamethylcyclohexasilane with silicon compounds. kinetics of some insertion reactions of dimethylsilylene
  作者：Iain M.T. Davidson、Naaman A. Ostah

  DOI：10.1016/s0022-328x(00)83467-1

  日期：1981.2

  Attempts to measure the kinetics of gas-phase insertion reactions of dimethylsilylene, generated by photolysis of dodecamethylcyclohexasilane, are described. Insertion of dimethylsilylene into silicon—hydrogen bonds was the main reaction with trimethylsilane, pentamethyldisilane, and sym-tetramethyldisilane; in all cases the activation energy for insertion was zero, and the rate constants were in the

  描述了尝试测量由十二甲基环己硅烷的光解所产生的二甲基甲硅烷基的气相插入反应的动力学的尝试。二甲基亚甲硅进-氢键的插入是用三甲基硅烷主反应，pentamethyldisilane，和符号-tetramethyldisilane; 在所有情况下，插入的活化能均为零，速率常数的比率为1：3.1：4.3。二甲基亚甲硅烷基也以28 kJ mol -1的活化能干净地插入氯化氢中。与甲基氯硅烷的光化学反应要复杂得多，几乎不涉及或不涉及甲硅烷基化学。这样发生的反应似乎几乎完全是通过根本机理进行的。