1,1,2,2-tetrakis(trimethylsilyl)-1,2-digermacyclohex-4-ene | 202214-16-2

• 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: 1,1,2,2-tetrakis(trimethylsilyl)-1,2-digermacyclohex-4-ene
• CAS: 202214-16-2
• 化学式: C₁₆H₄₂Ge₂Si₄
• 分子量: 492.031
• InChiKey: LBMBTFDKXJHCSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  1,1,2,2-tetrakis(trimethylsilyl)-dispiro[3,3',4,4'-biadamantane-1,2-digermacyclobutane] 、 1,3-丁二烯 以 正己烷 为溶剂， 以45%的产率得到1,1,2,2-tetrakis(trimethylsilyl)-1,2-digermacyclohex-4-ene
  参考文献：
  名称：

  Thermal and Photochemical [2+2] Cycloreversion of a 1,2-Disilacyclobutane and a 1,2-Digermacyclobutane

  摘要：

  Upon heating of the highly sterically congested 1,1,2,2-tetrakis(trimethylsilyl)dispiro[3,3',4,4'-biadamantane-1,2-disilacyclobutane] (2) in solution in the presence of trapping reagents, such as 1,3-butadienes, styrene, phenylacetylene, and methanol, the trapping products of the silene bis(trimethylsilyl)adamantylidenesilene (1) are formed with high regioselectivity and good yields. Photolysis of 2 at -196 degrees C in methylcyclohexane in the absence of trapping agents produces tetrakis(trimethylsilyl)disilene (3). Photolysis of 2 in solution in the presence of 1,3-butadiene leads to a 2:1 mixture of 1,1,2,2-tetrakis(trimethylsilyl)-1,2-disilacyclohex-4-ene (10)-the trapping product of the disilene 3-and of 1,1-bis(trimethylsilyl)-1-silocyclopent-3-ene (11)-the trapping product of bis(trimethylsilyl)silylene (4)-together with 2,2'-biadamantylidene. The results of laser flash photolysis and of additional trapping experiments suggest that the sole primary product in the photolysis of 2 is the disilene 3, which dissociates under further irradiation to produce the silylene 4. Heating of 1,1,2,2-tetrakis(trimethylsilyl)dispiro[3,3',4,4'-biadamantane-1,2-digermacyclobutane] (14) in solution results in the quantitative formation of 2,2'-biadamantylidene and of germanium-containing oligomers, while neither bis(trimethylsilyl)adamantylidenegermene (15) nor tetrakis(trimethylsilyl)digermene (16) or bis(trimethylsilyl)germylene (17) could be trapped. Upon photolysis 14 behaves similarly to 2, leading to 16 and 17, which could be trapped by 1,3-butadiene.

  DOI：

  10.1021/ja9729600

文献信息

• Thermal and Photochemical [2+2] Cycloreversion of a 1,2-Disilacyclobutane and a 1,2-Digermacyclobutane
  作者：Yitzhak Apeloig、Dmitry Bravo-Zhivotovskii、Ilya Zharov、Vladislav Panov、William J. Leigh、Gregory W. Sluggett

  DOI：10.1021/ja9729600

  日期：1998.2.1

  Upon heating of the highly sterically congested 1,1,2,2-tetrakis(trimethylsilyl)dispiro[3,3',4,4'-biadamantane-1,2-disilacyclobutane] (2) in solution in the presence of trapping reagents, such as 1,3-butadienes, styrene, phenylacetylene, and methanol, the trapping products of the silene bis(trimethylsilyl)adamantylidenesilene (1) are formed with high regioselectivity and good yields. Photolysis of 2 at -196 degrees C in methylcyclohexane in the absence of trapping agents produces tetrakis(trimethylsilyl)disilene (3). Photolysis of 2 in solution in the presence of 1,3-butadiene leads to a 2:1 mixture of 1,1,2,2-tetrakis(trimethylsilyl)-1,2-disilacyclohex-4-ene (10)-the trapping product of the disilene 3-and of 1,1-bis(trimethylsilyl)-1-silocyclopent-3-ene (11)-the trapping product of bis(trimethylsilyl)silylene (4)-together with 2,2'-biadamantylidene. The results of laser flash photolysis and of additional trapping experiments suggest that the sole primary product in the photolysis of 2 is the disilene 3, which dissociates under further irradiation to produce the silylene 4. Heating of 1,1,2,2-tetrakis(trimethylsilyl)dispiro[3,3',4,4'-biadamantane-1,2-digermacyclobutane] (14) in solution results in the quantitative formation of 2,2'-biadamantylidene and of germanium-containing oligomers, while neither bis(trimethylsilyl)adamantylidenegermene (15) nor tetrakis(trimethylsilyl)digermene (16) or bis(trimethylsilyl)germylene (17) could be trapped. Upon photolysis 14 behaves similarly to 2, leading to 16 and 17, which could be trapped by 1,3-butadiene.