1,4-bis(trimethylsilyl)dodecamethylbicyclo[2.2.2]octasilane | 79769-61-2

• 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: 1,4-bis(trimethylsilyl)dodecamethylbicyclo[2.2.2]octasilane
• 英文别名: bis(trimethylsilyl)-dodecamethylbicyclo[2.2.2]octasilane；(2,2,3,3,5,5,6,6,7,7,8,8-Dodecamethyl-4-trimethylsilyl-1,2,3,4,5,6,7,8-octasilabicyclo[2.2.2]octan-1-yl)-trimethylsilane
• CAS: 79769-61-2
• 化学式: C₁₈H₅₄Si₁₀
• 分子量: 551.482
• InChiKey: MOWYPCKJRUOCDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  3.0
• 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：

  1,4-bis(trimethylsilyl)dodecamethylbicyclo[2.2.2]octasilane 在 potassium tert-butylate 作用下， 以 乙二醇二甲醚 、 乙醚 为溶剂， 反应 1.0h， 生成 1-methoxycarbonyl-4-(trimethylsilyl)-dodecamethylbicyclo[2.2.2]octasilane
  参考文献：
  名称：

  Synthesis and Properties of Bridgehead-Functionalized Permethylbicyclo[2.2.2]octasilanes

  摘要：

  A series of previously unknown bridgehead-functionalized bicyclo[2.2.2]octasilanes, Me3Si-Si8Me12-X, X-Si8Me12-X, and X-Si8Me12-Y [X, Y = -SiMenPh3-n (n = 1, 2) (2, 3, 10), -SiMe(2)Fc (Fc = ferrocenyl) (4, 11, 13, 14), -COR (R = Me, tBu) (6, 7, 12), COOMe (8), COOH (9)], have been prepared by the reaction of the silanides Me3Si-Si8Me12-K+ or K+-Si8Me12-K+ with proper electrophiles and fully characterized. The molecular structures of 2, 3, 4, 6, 8, 9, 10, and 13 as determined by single-crystal X-ray diffraction analysis exhibit a slightly twisted structure of the bicyclooctasilane cage. Endocyclic bond lengths, bond angles, and dihedral angles are not influenced considerably by the substituents attached to the bridgehead silicon atoms. Due to sigma(SiSi)/pi(aryl) conjugation, a 20-30 nm bathochromic shift of the longest wavelength UV absorption band relative to Me3Si-Si8Me12-SiMe3 (1) is evident in the UV absorption spectra of the phenyl and ferrocenyl derivatives. Otherwise, UV absorption data do not support the assumption of aryl/aryl or aryl/C=O interaction via the sigma(SiSi) bicyclooctasilane framework.

  DOI：

  10.1021/om400184y
• 作为产物：
  描述：

  1,2-二溴-1,1,2,2-四甲基二硅烷 、 trans-1,4-bis(trimethylsilyl)octamethylcyclohexasilanyl-1,4-dipotassium*(18-crown-6)2 以 甲苯 为溶剂， 反应 2.0h， 以96%的产率得到1,4-bis(trimethylsilyl)dodecamethylbicyclo[2.2.2]octasilane
  参考文献：
  名称：

  重访Si 6号公路

  摘要：

  从1，4-二硅烷四硅烷开始，可以容易地获得1,1,4,4-四（三甲基甲硅烷基）八甲基环六硅烷。这可用于产生反式-1,4-二potassiocyclohexasilane。与镁的金属转移会导致阴离子硅原子之一的构型正式反转。取决于原料的立体化学构型，水解产生反式或顺式1,4-二氢环六硅烷。1，4-二potassiocyclohexasilane也为合成[2.2.0]，[2.2.1]和[2.2.2]双环低硅烷系统提供了方便的前体。笼形分子进一步功能化的主要可能性是通过1,4-双亚丙基-[2.2.2]-双环辛硅烷的合成和衍生化来证明的。对于双（三甲基甲硅烷基）双（十一碳甲基环六甲硅烷基）硅烷来说，三甲基甲硅烷基的裂解具有非凡的选择性，在含有16个硅-硅键的分子中，三甲基甲硅烷基被选择性地攻击。

  DOI：

  10.1016/j.jorganchem.2003.02.002

文献信息

• Rearrangement/Fragmentation Reactions of Oligosilanes with Aluminum Chloride
  作者：Harald Wagner、Judith Baumgartner、Christoph Marschner、Peter Poelt

  DOI：10.1021/om1011165

  日期：2011.8.8

  Reinvestigation of the Lewis acid catalyzed rearrangement of some open-chain permethyloligosilanes with the Al(Fe)Cl(3) catalyst system exhibited several cases of additional reactivity: namely, a fragmentation/cyclization reaction. Introduction of (trimethylsilyl)methyl substituents into the oligosilane substrates strongly facilitated this reaction, yielding cyclic or bicyclic carbacyclosilanes. Investigations concerning

  用Al（Fe）Cl（3）催化剂体系对路易斯酸催化的一些开链过甲基低聚硅烷的重排进行了重新研究，结果显示了几种其他反应性的情况：即片段化/环化反应。将（三甲基甲硅烷基）甲基取代基引入到低聚硅烷底物中极大地促进了该反应，产生了环状或双环的碳环硅烷。有关催化剂体系组成的研究表明，向AlCl（3）晶格中掺入约0.1％FeCl（3）可提供有效的催化剂。
• Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes
  作者：Haixing Li、Marc H. Garner、Zhichun Shangguan、Yan Chen、Qianwen Zheng、Timothy A. Su、Madhav Neupane、Taifeng Liu、Michael L. Steigerwald、Fay Ng、Colin Nuckolls、Shengxiong Xiao、Gemma C. Solomon、Latha Venkataraman

  DOI：10.1021/jacs.8b10296

  日期：2018.11.7

  linkers of varying length. We find an unusual variation of the single-molecule conductance among the four series at each linker length. We determine the relative conductance of the (bi)cyclic silicon structures by using the common length dependence of the four series rather than comparing the conductance at a single length. In contrast with the cyclic π-conjugated molecules, the conductance of σ-conjugated

  由于transoid构象中的强σ共轭，线性硅烷是有效的分子线；然而，硅烷单分子电导的构象依赖性的结构-功能关系仍未得到测试。在这里，我们报告了四个系列的官能化环状和双环硅烷的合成、电学测量和理论表征，包括环四硅烷、环戊硅烷、双环 [2.2.1] 庚硅烷和双环 [2.2.2] 八硅烷，它们都是由不同长度的线性硅连接器扩展。我们发现在每个接头长度的四个系列中单分子电导的异常变化。我们通过使用四个系列的共同长度依赖性而不是比较单个长度的电导来确定（双）环硅结构的相对电导。与环状 π 共轭分子相比，σ 共轭（双）环硅烷的电导由穿过分子的单一路径控制，并受沿该路径的二面角控制。这种对分子构象的强烈敏感性决定了 σ 共轭硅烷的单分子电导，并允许通过分子设计系统地控制电导。
• Synthesis and Properties of Bridgehead-Functionalized Permethylbicyclo[2.2.2]octasilanes
  作者：Harald Stueger、Bernd Hasken、Uwe Gross、Roland Fischer、Ana Torvisco Gomez

  DOI：10.1021/om400184y

  日期：2013.8.26

  A series of previously unknown bridgehead-functionalized bicyclo[2.2.2]octasilanes, Me3Si-Si8Me12-X, X-Si8Me12-X, and X-Si8Me12-Y [X, Y = -SiMenPh3-n (n = 1, 2) (2, 3, 10), -SiMe(2)Fc (Fc = ferrocenyl) (4, 11, 13, 14), -COR (R = Me, tBu) (6, 7, 12), COOMe (8), COOH (9)], have been prepared by the reaction of the silanides Me3Si-Si8Me12-K+ or K+-Si8Me12-K+ with proper electrophiles and fully characterized. The molecular structures of 2, 3, 4, 6, 8, 9, 10, and 13 as determined by single-crystal X-ray diffraction analysis exhibit a slightly twisted structure of the bicyclooctasilane cage. Endocyclic bond lengths, bond angles, and dihedral angles are not influenced considerably by the substituents attached to the bridgehead silicon atoms. Due to sigma(SiSi)/pi(aryl) conjugation, a 20-30 nm bathochromic shift of the longest wavelength UV absorption band relative to Me3Si-Si8Me12-SiMe3 (1) is evident in the UV absorption spectra of the phenyl and ferrocenyl derivatives. Otherwise, UV absorption data do not support the assumption of aryl/aryl or aryl/C=O interaction via the sigma(SiSi) bicyclooctasilane framework.
• Route Si6 revisited
  作者：Roland Fischer、Tina Konopa、Stephan Ully、Judith Baumgartner、Christoph Marschner

  DOI：10.1016/j.jorganchem.2003.02.002

  日期：2003.11

  functionalization of the cage molecules is demonstrated by the synthesis and derivatization of 1,4-dipotassio-[2.2.2]-bicyclooctasilane. The extraordinary selectivity for the cleavage of trimethylsilyl groups is demonstrated for the case of bis(trimethylsilyl)bis(undecamethylcyclohexasilanyl)silane, where in a molecule which contains 16 silicon–silicon bonds, a trimethylsilyl group is selectively attacked

  从1，4-二硅烷四硅烷开始，可以容易地获得1,1,4,4-四（三甲基甲硅烷基）八甲基环六硅烷。这可用于产生反式-1,4-二potassiocyclohexasilane。与镁的金属转移会导致阴离子硅原子之一的构型正式反转。取决于原料的立体化学构型，水解产生反式或顺式1,4-二氢环六硅烷。1，4-二potassiocyclohexasilane也为合成[2.2.0]，[2.2.1]和[2.2.2]双环低硅烷系统提供了方便的前体。笼形分子进一步功能化的主要可能性是通过1,4-双亚丙基-[2.2.2]-双环辛硅烷的合成和衍生化来证明的。对于双（三甲基甲硅烷基）双（十一碳甲基环六甲硅烷基）硅烷来说，三甲基甲硅烷基的裂解具有非凡的选择性，在含有16个硅-硅键的分子中，三甲基甲硅烷基被选择性地攻击。