tris(trimethylsilyl) cyanide | 131379-55-0

• 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: tris(trimethylsilyl) cyanide
• 英文别名: tris(trimethylsilyl)silylnitrile；Tris(trimethylsilyl)silylformonitrile
• CAS: 131379-55-0
• 化学式: C₁₀H₂₇NSi₄
• 分子量: 273.673
• InChiKey: WVOPNJZNAPRTBA-UHFFFAOYSA-N

物化性质

• 熔点：
  89 °C
• 沸点：
  234.9±23.0 °C(Predicted)
• 密度：
  0.829±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  C₁₉H₅₅GeNSi₈ 生成 tris(trimethylsilyl) cyanide
  参考文献：
  名称：

  [（Me3Si）3Si]2Ge⋅PMe3的炔烃加成和插入反应

  摘要：

  甲硅烷基化亚甲基-PMe 3加合物将其膦部分平稳地交换为N-杂环卡宾或异氰化物，从而形成各自的碱加合物。甲硅烷基化的亚甲基-PMe 3加合物与单取代炔烃的反应产生了带有插入Ge-Si键的炔烃的亚甲基加合物。对这一过程进行的计算研究为最初形成的紫丁香提供了证据，该紫丁烯重新排列为乙烯基亚锗烯。通过随后与PMe 3形成加合物来提供用于该反应的热力学驱动力。PMe 3的反应 双[（三甲基甲硅烷基）甲硅烷基]亚苄基与双取代炔烃的加成反应可形成稳定的细菌紫罗烯，可将其进一步异构化为西拉美身。

  DOI：

  10.1002/chem.201603317

文献信息

• NHC Adducts of Disilylated Germylenes and Stannylenes and Their Coordination Chemistry with Group 11 Metals
  作者：Małgorzata Walewska、Johann Hlina、Walter Gaderbauer、Harald Wagner、Judith Baumgartner、Christoph Marschner

  DOI：10.1002/zaac.201600284

  日期：2016.11

  Syntheses of NHC adducts of bis[tris(trimethylsilyl)silyl]germylene and -stannylene and some structurally related cyclic disilylated stannylenes are reported. Reactions of a cyclic stannylene NHC adduct with gold and silver cyanide led to cationic metal complexes with two cyanostannyl ligands. The Ag complex decomposed further to a cyanostannide. Reactions of bis[tris(trimethylsilyl)silyl]germylene

  报道了双 [三(三甲基甲硅烷基) 甲硅烷基] 亚甲基和亚锡基的 NHC 加合物的合成以及一些结构相关的环状二甲硅烷基化亚锡基。环状亚锡基 NHC 加合物与氰化金和银的反应生成了带有两个氰基锡烷基配体的阳离子金属配合物。Ag 络合物进一步分解为氰锡化物。双[三(三甲基甲硅烷基)甲硅烷基]二亚甲基和-亚锡基NHC加合物与金和氰化银的反应显示出更不寻常的配位化学，亚苯基单元的一个甲硅烷基被转移到第11族金属。
• Catalyst-free visible light-promoted defunctionalization of alkyl isocyanides with a hydrosilane through C–N bond cleavage
  作者：Yu-Qing Ma、Shi-Kai Tian

  DOI：10.1039/d4ob00173g

  日期：——

  A radical initiator-free defunctionalization reaction of alkyl isocyanides with a hydrosilane has been established through C–N bond cleavage under catalyst-free visible light irradiation. Various alkyl isocyanides participated in the defunctionalization with tris(trimethylsilyl)silane under blue light irradiation at room temperature, delivering the reduced products in good yields with high chemoselectivity

  在无催化剂的可见光照射下，通过 C-N 键断裂，建立了烷基异氰化物与氢硅烷的无自由基引发剂去官能化反应。各种烷基异氰化物在室温蓝光照射下参与三(三甲基甲硅烷基)硅烷的去官能化，以良好的收率和高化学选择性提供还原产物。
• Isonitriles as Alkyl Radical Precursors in Visible Light Mediated Hydro‐ and Deuterodeamination Reactions**
  作者：Irene Quirós、María Martín、Miguel Gomez‐Mendoza、María Jesús Cabrera‐Afonso、Marta Liras、Israel Fernández、Luis Nóvoa、Mariola Tortosa

  DOI：10.1002/anie.202317683

  日期：2024.2.12

  We report the use of isonitriles as alkyl radical precursors in visible-light mediated hydro- and deuterodeamination reactions. Most examples only require visible-light irradiation of the isonitrile in the presence of a silyl radical precursor, although a significant acceleration was observed in the presence of an organic photocatalyst. The method is scalable, shows broad functional group compatibility

  我们报道了在可见光介导的加氢和氘代脱氨基反应中使用异腈作为烷基自由基前体。大多数例子仅需要在甲硅烷基自由基前体存在下对异腈进行可见光照射，尽管在有机光催化剂存在下观察到显着的加速。该方法具有可扩展性，显示出广泛的官能团兼容性，并且适用于 C α伯、C α仲和 C α叔烷基异腈。
• Tris(trimethylsilyl)silane as a radical-based reducing agent in synthesis
  作者：M. Ballestri、C. Chatgilialoglu、K. B. Clark、D. Griller、B. Giese、B. Kopping

  DOI：10.1021/jo00002a035

  日期：1991.1

  Tris(trimethylsilyl)silane is an effective reducing agent for organic halides, selenides, xanthates, and isocyanides, as well as an effective hydrosilylating agent for dialkyl ketones and alkenes. The silane functions as a mediator in the formation of intermolecular carbon-carbon bonds via radicals and allows a variety of organic substrates to be used as alkyl radical percursors. Absolute rate constants for the reaction of (Me3Si)3Si radicals with a variety of organic compounds have been measured in solution by laser flash photolysis. At 294 K rate constants are > 5 x 10(7) M-1 s-1 for C = C double bonds that are activated by neighboring pi-electron systems or by electron-withdrawing groups. For other substrates, reactivities decreased in the order xanthate > selenide > isocyanide > nitro > sulfide.
• BALLESTRI, M.;CHATGILIALOGLU, C.;CLARK, K. B.;GRILLER, D.;GIESE, B.;KOPPI+, J. ORG. CHEM., 56,(1991) N, C. 678-683
  作者：BALLESTRI, M.、CHATGILIALOGLU, C.、CLARK, K. B.、GRILLER, D.、GIESE, B.、KOPPI+

  DOI：——

  日期：——