1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne

• 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: 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne
• 化学式: C₃₄H₉₀Si₁₂
• 分子量: 836.115
• InChiKey: OOKFNRALXGTIRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.52
• 重原子数：
  46
• 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：

  1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 以 四氢呋喃 、 甲苯 为溶剂， 反应 6.0h， 生成 C₃₅H₉₆OSi₁₂
  参考文献：
  名称：

  Hydroboration of Disilyne RSi≡SiR (R = SiⁱPr[CH(SiMe₃)₂]₂), Giving Boryl-Substituted Disilenes

  摘要：

  The reaction of 1,1,4,4-tetralds[bis-(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne (1) with hydroboranes afforded boryl-substituted disilenes R(R'B-2)Si=SiHR 3a and 3b (R = (SiPr)-Pr-i[CH(SiMe3)(2)](2), R'B-2 = 9-borabicyclo[3.3.1]nonan-9-yl (3a), catecholboryl (3b)). Spectroscopic and X-ray crystallographic analyses of 3a and 3b showed that 3a has a nearly coplanar arrangement of the Si=Si double bond and the boryl group, allowing pi-conjugation between them, whereas 3b, with a markedly twisted arrangement, exhibits no such conjugation. Theoretical calculations suggest that pi-conjugation between the pi-orbital of the Si=Si double bond and the vacant 2p-orbital on the boron atom is markedly influenced by the dihedral angle between the Si=Si double-bond plane and boryl group plane.

  DOI：

  10.1021/om200106h

文献信息

• Reaction of a diaryldigermyne with ethylene
  作者：Takahiro Sasamori、Tomohiro Sugahara、Tomohiro Agou、Koh Sugamata、Jing-Dong Guo、Shigeru Nagase、Norihiro Tokitoh

  DOI：10.1039/c5sc01266j

  日期：——

  Reaction of a stable digermyne with ethylene afforded the corresponding 1,2-digermacyclobutene. Depending on the reaction conditions applied, further reaction of this 1,2-digermacyclobutene with ethylene furnished two different reaction products: a 1,4-digerma-bicyclo[2.2.0]hexane or a bis(germiranyl)ethane.

  稳定的二锗烯与乙烯发生反应，生成相应的1,2-二锗环丁烯。根据所施加的反应条件，这种1,2-二锗环丁烯与乙烯的进一步反应会产生两种不同的产物：1,4-二锗-双环[2.2.0]己烷或双(锗烷基)乙烷。
• A New Disilene with π-Accepting Groups from the Reaction of Disilyne RSi≡SiR (R = Si^<i>i</i>Pr[CH(SiMe₃)₂]) with Isocyanides
  作者：Katsuhiko Takeuchi、Masaaki Ichinohe、Akira Sekiguchi

  DOI：10.1021/ja212065a

  日期：2012.2.15

  corresponding disilyne-isocyanide adducts [RSiSiR(CNR')(2)] (R = Si(i)Pr[CH(SiMe(3))(2)](2), R' = (t)Bu (2a) or CMe(2)CH(2)(t)Bu (2b)), which are stable below -30 °C and were characterized by spectroscopic data and, in the case of 2a, X-ray crystallography. Upon warming to room temperature, 2 underwent thermal decomposition to produce 1,2-dicyanodisilene R(NC)Si═Si(CN)R (3) and 1,2-dicyanodisilane R(NC)HSiSiH(CN)R

  1,1,4,4-四[​​双(三甲基甲硅烷基)甲基]-1,4-二异丙基四硅-2-炔(1)与叔丁基异氰化物或叔辛基异氰化物反应生成相应的二甲硅烷-异氰化物加合物[RSiSiR( CNR')(2)] (R = Si(i)Pr[CH(SiMe(3))(2)](2), R' = (t)Bu (2a) 或 CMe(2)CH(2) (t)Bu (2b))，在 -30 °C 以下稳定，并通过光谱数据表征，在 2a 的情况下，X 射线晶体学表征。升温至室温后，2 发生热分解，生成 1,2-二氰二硅烷 R(NC)Si=Si(CN)R (3) 和 1,2-二氰二硅烷 R(NC)HSiSiH(CN)R (4)烷烃和烯烃的 CN 键断裂和消除。1,2-二氰二硅烯衍生物 3 的特征是 X 射线晶体学。
• Unusual Reactivity of a Disilyne with 4-Dimethylaminopyridine: Formation of an Intramolecularly N-Coordinated Silylene and Its Isomerization to a Zwitterionic Silyl Anion
  作者：Torahiko Yamaguchi、Akira Sekiguchi

  DOI：10.1021/ja202605x

  日期：2011.5.18

  4-dimethylaminopyridine unexpectedly produced the intramolecularly N-coordinated silylene 2 as the primary product. However, 2 was not thermally stable at room temperature in solution and slowly isomerized to silyl anion 3 with a zwitterionic structure via 1,2-hydrogen migration followed by Si-N bond formation.

  可分离的 1,1,4,4-四[​​双（三甲基甲硅烷基）甲基]-1,4-二异丙基四硅-2-炔（1）与等量的 4-二甲氨基吡啶的反应出人意料地产生了分子内 N-配位的亚甲硅烷基 2，如主要产品。然而，2在室温下在溶液中不是热稳定的，并且通过1,2-氢迁移随后形成Si-N键缓慢异构化为具有两性离子结构的甲硅烷基阴离子3。
• Reactivity of a Disilyne RSi≡SiR (R = Si<i>ⁱ</i>Pr[CH(SiMe₃)₂]₂) toward π-Bonds:  Stereospecific Addition and a New Route to an Isolable 1,2-Disilabenzene
  作者：Rei Kinjo、Masaaki Ichinohe、Akira Sekiguchi、Nozomi Takagi、Michinori Sumimoto、Shigeru Nagase

  DOI：10.1021/ja072759h

  日期：2007.6.1

  thylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 with cis- and trans-butenes produced cis- and trans-3,4-dimethyl-1,2-disilacyclobutenes 2a and 2b, respectively. The reactions proceeded in a stereospecific manner. Theoretical calculations on the reaction between 1 and 2-butenes show that the reaction proceeds via the interaction between the LUMO (πin*) of 1 and the HOMO of 2-butene, resulting in

  1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 与顺式和反式丁烯反应生成顺式和反式-3,4-二甲基-1 ,2-二杂环丁烯分别为 2a 和 2b。反应以立体特异性方式进行。1 和 2-丁烯之间反应的理论计算表明，反应通过 1 的 LUMO (πin*) 和 2-丁烯的 HOMO 之间的相互作用进行，导致正式的 [1 + 2] 环加成得到硅杂环丙基-甲硅烷基中间体，然后进行扩环以产生最终产品。1 与苯乙炔反应生成 1,2-二硅杂苯衍生物，作为两种区域异构体的混合物，其中一种通过 X 射线晶体学表征。3a 的 1,2-二硅苯的六元环几乎是平面的，Si-Si 键长为 2。
• Reactivity of the disilyne RSiSiR (R = Si^<i>i</i> Pr[CH(SiMe₃ )₂ ]₂ ) toward bis(silylcyanide) forming a 1,4-diaza-2,3-disilabenzene analog
  作者：Katsuhiko Takeuchi、Masaaki Ichinohe、Akira Sekiguchi、Jing-Dong Guo、Shigeru Nagase

  DOI：10.1002/poc.1617

  日期：2010.4

  The reaction of 1,1,4,4‐tetrakis[bis(trimethylsilyl)methyl]‐1,4‐diisopropyl‐2‐tetrasilyne 1 with 1,3‐bis(cyanodimethylsilyl)propane 4 produced the 1:1 adduct, 1,4‐diaza‐2,3‐disilabenzene analog 5 as deep red crystals, which was characterized by spectroscopic data and X‐ray crystallography. Theoretical calculations on the reaction between the disilyne and silylcyanide show that the reaction proceeds

  1,1,4,4-四[​​双（三甲基硅烷基）甲基] -1,4-二异丙基-2-四硅炔1与1,3-双（氰基二甲基硅烷基）丙烷4的反应生成了1：1的加合物，1， 4-重氮杂2,3-二硅二苯类似物5为深红色晶体，通过光谱数据和X射线晶体学表征。在disilyne和silylcyanide表明通过在反应进行的反应的理论计算σ silylcyanide的-coordination，其中silylcyanide的两个分子与disilyne的SP-硅原子坐标，使Ç  C键的形成。版权所有©2009 John Wiley＆Sons，Ltd.