3,4-dimethyl-1,1-dichlorogermacyclopent-3-ene | 5764-65-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: 3,4-dimethyl-1,1-dichlorogermacyclopent-3-ene
• 英文别名: 3,4-dimethyl-1-germacyclopent-3-ene；1-Germano-3,4-dimethyl-cyclopent-3-en；3,4-Dimethylgermacyclopentene-3；3,4-dimethyl-2,5-dihydro-1H-germole
• CAS: 5764-65-8
• 化学式: C₆H₁₂Ge
• 分子量: 156.751
• InChiKey: XCKYMZAQQDTEDQ-UHFFFAOYSA-N

物化性质

• 沸点：
  25 °C(Press: 4 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  1.34
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  3,4-dimethyl-1,1-dichlorogermacyclopent-3-ene 以 gas 为溶剂， 生成 germanium dihydride
  参考文献：
  名称：

  germ烯和二甲基亚锗烯与二甲基锗烷反应的绝对速率常数：重碳烯中甲基的钝化作用

  摘要：

  标题反应的气相速率常数已通过使用光前体，GeH 2的3,4-二甲基-1-锗环戊-3-烯和GeMe 2的五甲基二茂铁在297 K下通过激光快速光解获得。获得的值为（）：对于GeH 2为（2.38±0.11）×10 -10，对于GeMe 2为（2.26±0.10）×10 -13。这些结果表明，GeMe 2在Me 2 GeH 2的GeH键中的插入反应比GeH 2慢1050倍。。这是根据涉及中间H-桥联配合物的一般机理来解释的，该机理适用于亚甲硅烷基和亚二甲基亚砜的插入。对于GeMe 2插入，反应物与配合物处于平衡状态，该配合物在速率控制步骤中重新排列为产物。

  DOI：

  10.1016/s0009-2614(01)01257-x
• 作为产物：
  描述：

  2,3-二甲基-1,3-丁二烯 以 四氢呋喃 、 乙醚 为溶剂， 反应 13.0h， 生成 3,4-dimethyl-1,1-dichlorogermacyclopent-3-ene
  参考文献：
  名称：

  通过聚（环锗戊烯）进行锗光图案化

  摘要：

  通过1,1-二氢环锗戊烯单体的脱氢偶联制备了一系列空气稳定的聚（环锗戊烯） 。将所得聚锗烷暴露于紫外光导致从聚合物侧链中消除有机丁二烯并沉积锗金属。总的来说，这项研究介绍了一种温和的方法来获得用于光电应用的半导体 Ge 图案。

  DOI：

  10.1039/d3cc01708g

文献信息

• Direct Time-Resolved Study of the Gas-Phase Reactions of Germylene with Ethyl- and Diethylgermane:  Absolute Rate Constants, Temperature Dependences, and Mechanism
  作者：Rosa Becerra、Sergey E. Boganov、Mikhail P. Egorov、Irina V. Krylova、Oleg M. Nefedov、Robin Walsh

  DOI：10.1021/jp0661948

  日期：2007.3.1

  Time-resolved studies of germylene, GeH2, generated by the 193 nm laser flash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reactions with ethyl- and diethylgermanes in the gas phase. The reactions were studied over the pressure range 1-100 Torr with SF6 as bath gas and at five temperatures in the range 297-564 K. Only slight pressure

  进行了时间分辨的3,4-二甲基-1-germacyclopent-3-ene的193 nm激光闪光光解产生的亚甲基锗酸GeH2的研究，以求得其与乙基和二乙基锗烷的双分子反应的速率常数。气相。在1-6 Torr的压力范围内，以SF6作为熔池气体，并在297-564 K的五个温度下对反应进行了研究。GeH2+ EtGeH3（399、486和564 K）的压力依赖性很小。高压速率常数给出以下Arrhenius参数：对于GeH2 + EtGeH3，log A = -10.75 +/- 0.08，Ea = -6.7 +/- 0.6 kJ mol-1；对于GeH 2 + Et 2 GeH 2，log A = -10.68 +/- 0.11，Ea = -6.95 +/- 0.80 kJ mol-1。这些与298 K时快速，近碰撞控制的关联过程一致。RRKM建模计算大部分是：与观察到的GeH2 + EtG
• Controlled Growth of Dichlorogermanium Oligomers from Lewis Basic Hosts
  作者：S. M. Ibrahim Al-Rafia、Mohammad R. Momeni、Robert McDonald、Michael J. Ferguson、Alex Brown、Eric Rivard

  DOI：10.1002/anie.201302767

  日期：2013.6.17

  To branch or not to branch: A mild stepwise route to various linear and branched (GeCl2)x oligogermylenes supported by Lewis bases is reported, including the carbene‐bound Ge4 complex NHC⋅GeCl2Ge(GeCl3)2 (see picture). Dipp=2,6‐iPr2C6H3, NHC=N‐heterocyclic carbene.

  到分支或不分支：温和逐步路由到各种线性和支链的（GeCl 2）X通过路易斯碱支持oligogermylenes据悉，包括卡宾结合的Ge 4复杂NHC⋅GeCl 2葛（GeCl 3）2（参见图片）。Dipp = 2,6- i Pr 2 C 6 H 3，NHC = N-杂环卡宾。
• Time-resolved gas-phase kinetic study of the reaction of germylene with propene over the temperature range 293–415 K: the thermal stabilities of germiranes
  作者：Rosa Becerra、Robin Walsh

  DOI：10.1016/s0022-328x(01)00839-7

  日期：2001.11

  Absolute rate constants have been obtained for the title reaction over the pressure range 1–100 Torr (in SF6 bath gas) and the temperature range 293–415 K, by means of laser flash photolysis to generate and monitor germylene, GeH2. The reaction showed the characteristic pressure dependence of a third-body assisted association reaction. The high pressure rate constants, obtained by extrapolation, gave

  通过激光闪光光解法生成并监测二甲基亚甲基GeH 2，可以在压力范围为1-100 Torr（在SF 6浴液中）和温度范围为293-415 K的条件下获得标题反应的绝对速率常数。该反应显示出第三体辅助缔合反应的特征压力依赖性。通过外推法获得的高压速率常数给出了Arrhenius方程：该参数对应于在℃时发生的快速反应。室温下有59％的碰撞率。GeH 2π加成的碰撞效率不小于SiH 2的碰撞效率。RRKM（Rice，Ramsperger，Kassel，Marcus）模型基于与动力学一致的变化过渡态，非常适合数据，E o = 105 kJ mol -1的值对应于ΔH °= 122用于2-甲基锗烷分解的±12 kJ mol -1。该结果与其他工作一起表明，C-甲基取代会降低生殖环的热稳定性，并且生殖环约为。50–60 kJ mol -1的分解稳定性不如硅烷硅烷。
• Synthesis and reactivity of germanium heterocycles containing germanium-tin bonds
  作者：K. S. Nosov、A. V. Lalov、A. S. Borovik、V. Va. Lee、M. P. Egorov、O. M. Nefedov

  DOI：10.1007/bf01431129

  日期：1996.11

  Previously unknown stannyl-substituted germanium heterocycles, 1,1-bis(trimethylstannyl)-2,3,4, 5-tetraphenyl-1-germacyclopenta-2,4-diene and 1,1-bis(trimethylstannyl)-3,4-dimethyl-1-germacyclopent-3-ene were synthesized, and their photolysis and chemical transformations were studied.
• Reaction of Germylene with Sulfur Dioxide: Gas-Phase Kinetic and Theoretical Studies
  作者：Rosa Becerra、J. Pat Cannady、Robin Walsh

  DOI：10.1021/om500842v

  日期：2014.11.24

  Time-resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene at 193 nm, have been carried out to obtain rate constants for its bimolecular reaction with SO2. The reaction was studied in the gas phase, mainly at a total pressure of 10 Torr (in SF6 bath gas) at five temperatures in the range 295553 K. Pressure variation measurements over the range 1100 Torr (SF6) at 295, 408, and 553 K revealed no pressure dependence. The second-order rate constants at 10 Torr (SF6 bath gas) fit the Arrhenius equation log(k/cm(3) molecule(1) s(1)) = (-11.01 +/- 0.09) + (4.62 +/- 0.65 kJ mol(1))/RT ln 10, where the uncertainties are single standard deviations. The collisional efficiency is 19% at 298 K, and in kinetic terms the reaction resembles that of SiH2 with SO2 quite closely. Quantum chemical calculations at the B3LYP/aug-cc-pvQZ level suggest a mechanism occurring via the initial addition of GeH2 to one O atom of SO2 to form H2GeOSO which, via a 1,3-H shift followed by a cyclization, leads to a four-membered-ring species, cyclo-HGeO2SH(cis). A low-energy H2 elimination results in the formation of cyclo-GeO2S, a hitherto unknown compound. A number of other species on the enthalpy surface have been identified, including the novel Ge(OH)(2)S-..., a cyclic five-membered ring comprising an S atom stabilized by dihydroxygermylene. However, none of these other molecules seem to be involved as intermediates in this reaction, either because barriers to their formation or rearrangement are too high or because their enthalpies are insufficiently negative for them to be collisionally stabilized under experimental conditions. The reaction is compared and contrasted with that of SiH2 + SO2.