2-germa-1,1,3,3-tetrakis(trimethylsilyl)-2,2,3,3-tetramethylcyclopentasilan-2-ylidene - triethylphosphane adduct | 1436417-22-9

• 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: 2-germa-1,1,3,3-tetrakis(trimethylsilyl)-2,2,3,3-tetramethylcyclopentasilan-2-ylidene - triethylphosphane adduct
• CAS: 1436417-22-9
• 化学式: C₂₂H₆₃GePSi₈
• 分子量: 655.99
• InChiKey: WNGNNEPEBMJICC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.44
• 重原子数：
  32.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  2-germa-1,1,3,3-tetrakis(trimethylsilyl)-2,2,3,3-tetramethylcyclopentasilan-2-ylidene - triethylphosphane adduct 在 三(五氟苯基)硼烷 作用下， 以 正戊烷 为溶剂， 反应 2.0h， 以64%的产率得到1,2-digerma-1,2,3,3,6,7,10,10-octakis(trimethylsilyl)octamethyltricyclo[5.3.0.0^2,6]decasilane
  参考文献：
  名称：

  环状二甲硅烷基化和二芽基化锗烯

  摘要：

  环状二甲硅烷基或甲锗烷基digermylated的三乙基加成物的制备是通过1,4- dipotassio-1,1,4,4-四（三甲基硅烷基）tetramethyltetrasilane的反应与GEBR实现2 ·（二恶烷）和PET 3。B(C 6 F 5 ) 3 的膦提取允许形成无碱的亚锗烯，其经历 1,2-三甲基甲硅烷基转移到亚锗烯原子以形成各自的硅锗烯或二锗烯，其在 [2 + 2] 环加成中进一步二聚化到三环化合物。在理论研究中阐明了与先前研究的类似的亚锡基和铅基相比，亚锗烯的反应性完全不同的原因。

  DOI：

  10.1021/om400365v
• 作为产物：
  描述：

  1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane 、 dibromogermane dioxane 、 三乙基膦 以 四氢呋喃 、 乙二醇二甲醚 为溶剂， 反应 12.0h， 以71%的产率得到2-germa-1,1,3,3-tetrakis(trimethylsilyl)-2,2,3,3-tetramethylcyclopentasilan-2-ylidene - triethylphosphane adduct
  参考文献：
  名称：

  环状二甲硅烷基化和二芽基化锗烯

  摘要：

  环状二甲硅烷基或甲锗烷基digermylated的三乙基加成物的制备是通过1,4- dipotassio-1,1,4,4-四（三甲基硅烷基）tetramethyltetrasilane的反应与GEBR实现2 ·（二恶烷）和PET 3。B(C 6 F 5 ) 3 的膦提取允许形成无碱的亚锗烯，其经历 1,2-三甲基甲硅烷基转移到亚锗烯原子以形成各自的硅锗烯或二锗烯，其在 [2 + 2] 环加成中进一步二聚化到三环化合物。在理论研究中阐明了与先前研究的类似的亚锡基和铅基相比，亚锗烯的反应性完全不同的原因。

  DOI：

  10.1021/om400365v

文献信息

• Coordination Chemistry of Disilylated Germylenes with Group 4 Metallocenes
  作者：Johann Hlina、Judith Baumgartner、Christoph Marschner、Patrick Zark、Thomas Müller

  DOI：10.1021/om400215v

  日期：2013.6.10

  germylene NHC titanocene complex. This complex was, however, obtained in the reaction of Cp2Ti(btmsa) with the NHC germylene adduct. A computational analysis of the structure of the group 4 metallocene germylene complexes revealed the multiple-bond character of the M–Ge(II) linkage, which can be rationalized with the classical σ-donor/π-acceptor interaction. The strength of the M–Ge(II) bond increases descending

  在镁的存在下二甲硅烷基化五元环状亚锗烷基的 PEt 3加合物与第 4 族茂金属二氯化物的反应导致形成钛、锆和铪各自的亚锗烯茂金属膦配合物。尝试在相同条件下使二甲硅烷基化四元环状亚锗烷基的相关 NHC 加合物与 Cp 2 TiCl 2 反应没有得到预期的亚锗烯 NHC 二茂钛复合物。然而，该配合物是在 Cp 2的反应中获得的Ti(btmsa) 与 NHC 锗烯加合物。对第 4 族茂金属锗烯配合物结构的计算分析揭示了 M-Ge(II) 键的多键特性，这可以通过经典的 σ-供体/π-受体相互作用来合理化。M-Ge(II) 键的强度增加了下降的第 4 族。
• Spirocyclic germanes <i>via</i> transannular insertion reactions of vinyl germylenes into Si–Si bonds
  作者：Małgorzata Walewska、Judith Baumgartner、Christoph Marschner、Lena Albers、Thomas Müller

  DOI：10.1039/c8dt00315g

  日期：——

  The reactions of two cyclic germylene phosphane adducts with monosubstituted acetylenes caused the formation of spirocyclic germanes, which is postulated to occur by double acetylene insertion into germylene attached bonds. Further insertion of the formed cyclic divinylgermylene into transannular Si–Si or Si–Ge bonds provides the spirocyclic germanes. Thermal treatment of two germacyclopropenes, formed

  两个环状亚锗烷基膦加合物与单取代乙炔的反应导致形成螺环锗烷，这被认为是通过双乙炔插入亚锗烷基连接键而发生的。将形成的环状二乙烯基锗烯进一步插入到跨环状 Si-Si 或 Si-Ge 键中提供了螺环锗烷。通过两个环状亚锗烷基膦加合物与甲苯的反应形成的两种锗环丙烯的热处理也产生螺环锗烷。然而，后者的结构需要更复杂的机械建议。
• Basic Reactivity Pattern of a Cyclic Disilylated Germylene
  作者：Małgorzata Walewska、Johann Hlina、Judith Baumgartner、Thomas Müller、Christoph Marschner

  DOI：10.1021/acs.organomet.6b00482

  日期：2016.8.22

  In order to estimate the reactivity of disilylated germylene phosphine adducts, a cyclic version of this compound class was reacted with a number of different reagents. Reactions with the chalcogens sulfur, selenium, and tellurium led to dimers of the heavy ketone analogues. Reactions with water and ethyl bromide proceeded to give the respective oxidized germanol and germyl bromide. Two different reactions with alkynes were observed which led either to a germacyclopropene, by addition of tolane to the germylene, or to a silagermacyclobutene, likely formed by addition of the alkyne across a silagermene. Reaction via the silagermene was also observed in the reaction with benzophenone. Reaction of a germylene phosphine adduct with GeCl2 center dot(dioxane) provided insertion of the silylated germyle into a Ge-Cl bond, leading to a germylated chlorogermylene phosphine adduct.
• Coordination Chemistry of Cyclic Disilylated Germylenes and Stannylenes with Group 11 Metals
  作者：Johann Hlina、Henning Arp、Małgorzata Walewska、Ulrich Flörke、Klaus Zangger、Christoph Marschner、Judith Baumgartner

  DOI：10.1021/om500668r

  日期：2014.12.22

  Reactions of Et3P adducts of bissilylated germylenes and stannylenes with gold, silver, and copper cyanides led to cyanogermyl or -stannyl complexes of the respective metals. In the course of the reaction the phosphine moved to the metal, while the cyanide migrated to the low-coordinate group 14 element. The respective gold complexes were found to be monomeric, whereas the silver and copper complexes exhibited a tendency to dimerize in the solid state. Attempts to abstract the phosphine ligand with B(C6F5)(3) led only to the formation of adducts with the borane coordinating to the cyanide nitrogen atom.