octamethyltetrasilacyclohexyne | 138542-16-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: octamethyltetrasilacyclohexyne
• 英文别名: 1,1,2,2,3,3,4,4-octamethyl-1,2,3,4-tetrasilacyclohex-5-yne
• CAS: 138542-16-2
• 化学式: C₁₀H₂₄Si₄
• 分子量: 256.643
• InChiKey: HCAVAUJCKNVYCB-UHFFFAOYSA-N

物化性质

• 沸点：
  204.4±23.0 °C(Predicted)
• 密度：
  0.85±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  octamethyltetrasilacyclohexyne 在 potassium diazodicarboxylate 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 正己烷 为溶剂， 反应 2.0h， 生成 1,1,2,2,3,3,4,4-Octamethyl-1,2,3,4-tetrasilacyclohexane
  参考文献：
  名称：

  Conformational Effects in Photoelectron Spectra of Tetrasilanes

  摘要：

  Four cyclic carbosilanes [(SiMe2)(4)(CH2)(n)], n = 1-4 (1-4), have been synthesized and used as models of conformationally constrained tetrasilane. Results of matrix isolation IR spectroscopy, annealing, and photodestruction, combined with HF/3-21G* calculations on low-energy conformers, suggest that in each each compound the SiSiSiSi dihedral angle omega is constrained within relatively narrow Limits: 1, 0 degrees; 2, 35-55 degrees; 3, 45-65 degrees (30 degrees for a higher-energy conformer); and 4, 60-80 degrees. It is argued that other structural differences between 1-4 and the linear chain analogue, decamethyltetrasilane Si4Me10 (5), are of secondary importance, that Koopmans' theorem can be used within a family of closely related structures, and that measurements of photoelectron spectra of 1-5 permit the construction of an experimental counterpart to the orbital energy correlation diagram for the syn-anti conformational transformation in tetrasilane. The trends found for the first three ionization potentials, assigned to electron removal from the three sigma(SiSi) molecular orbitals, are readily understood qualitatively by reference to the ladder C model of saturated chain structure. They show clearly that the even simpler Sandorfy C model is not appropriate for the description of sigma conjugation in saturated systems.

  DOI：

  10.1021/jp970693e
• 作为产物：
  描述：

  1,4-dichloropermethyltetrasilane 、 二锂乙炔化物 以65%的产率得到octamethyltetrasilacyclohexyne
  参考文献：
  名称：

  四硅杂环己炔的合成与结构

  摘要：

  尽管应变环炔烃多年来一直受到大量实验和理论的关注，但最小的可分离环是七元环。4 我们在此报告第一个可分离 5 六元环的合成、化学和结构表征以及从头计算-碳三键。学科化学评论经美国化学学会杂志 114 (1992): 4920, doi:10.1021/ja00038a077 许可重印（改编）。版权所有 1992 美国化学学会。本文可在爱荷华州立大学数字资源库中获取：http://lib.dr.iastate.edu/chem_pubs/252 4920 J. Am。陈。社会。1992, 114, 492Q-4921 这些原子，与 772-桥接 CO 配体的其他例子相反。1•3•14 每个配体作为一个四电子供体。两个电子由碳原子提供给它桥接的一对金属原子，来自氧的两个电子提供给金属 Ru(8)。由于两个桥连羰基配体的氧原子键合到同一个金属原子上，碳原子被带入异常紧密的非键合接触：C(53).

  DOI：

  10.1021/ja00038a077

文献信息

• Reaction of Polysilacycloalkynes with CpCo(CO)₂ and CpMn(CO)₃
  作者：Fusao Hojo、Kyoko Fujiki、Wataru Ando

  DOI：10.1021/om960056v

  日期：1996.8.6

  Reactions of a pentasilacycloheptyne and a hexasilacyclooctyne with CpCo(CO)2 resulted in facile formation of metallapentene derivatives, and a tetrasilacyclohexyne gave a triene derivative. Photochemical reactions of CpMn(CO)3 with the tetrasilacyclohexyne and the hexasilacyclooctyne gave vinylidene complexes. The vinylidene complex readily reacts with tetrasilacyclohexyne to yield the triene and a

  五硅环环庚炔和六硅环辛炔与CpCo（CO）2的反应导致金属lapentene衍生物的容易形成，四硅环己炔产生三烯衍生物。CpMn（CO）3与四硅氮杂环己炔和六硅氮杂环辛炔的光化学反应产生了亚乙烯基配合物。亚乙烯基配合物容易与四硅杂环丁烯反应，生成三烯和双（丙二烯）衍生物。通过X射线晶体学分析确定金属lapentenes和双（allen）之一的结构。
• First isolation of six-membered cyclic acetylene: synthesis and reaction of tetrasilacyclohexynes
  作者：Wataru Ando、Fusao Hojo、Sachie Sekigawa、Nobuko Nakayama、Toshio Shimizu

  DOI：10.1021/om00039a002

  日期：1992.3

  Six-membered cyclic acetylenes, namely 1,1,2,2,3,3,4,4-octaalkyl-1,2,3,4-tetrasilacyclohexynes (1), have been synthesized directly by the reaction of 1,4-dichlorooctaalkyltetrasilanes with acetylene di-Grignard reagent followed by GC purification. It is found that the tetrasilacyclohexyne 1a is thermally stable: t1/2 = 8 h (decane, 174-degrees-C). Reactions of 1a with dicobalt octacarbonyl, 2,3-dimethyl-1,3-butadiene, phenyl azide, and diphenyldiazomethane give the corresponding cyclo-adducts, respectively.