tetrakis(trimethylsilyl)disilene | 69545-88-6

• 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: tetrakis(trimethylsilyl)disilene
• 英文别名: 2-Tetrasilene, 1,1,1,4,4,4-hexamethyl-2,3-bis(trimethylsilyl)-；[bis(trimethylsilyl)silylidene-trimethylsilylsilyl]-trimethylsilane
• CAS: 69545-88-6
• 化学式: C₁₂H₃₆Si₆
• 分子量: 348.931
• InChiKey: MHFKWNQMSJWTRY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.72
• 重原子数：
  18
• 可旋转键数：
  4
• 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：

  甲醇 、 tetrakis(trimethylsilyl)disilene 在 other trapping compounds 作用下， 以 异辛烷 为溶剂， 生成 2-[bis(trimethylsilyl)methoxysilyl]adamantane
  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
• 作为产物：
  描述：

  octakis(trimethylsilyl)cyclotetrasilane 以 甲基环己烷 为溶剂， 生成 tetrakis(trimethylsilyl)disilene
  参考文献：
  名称：

  环四硅烷的光解。对分子结构的显着依赖

  摘要：

  环四硅烷的光解反应是通过在293 K的甲基环己烷（MCH）中进行激光闪光光解，以及在77 K的甲基环己烷-异戊烷（MP; 3：1，v / v）玻璃中进行稳态光解。关于环四硅烷的分子结构。平面的全甲硅烷基环四硅烷1和2生成相应的二硅酮（D1和D2），在293 K处的410 nm和77 K下的415 nm处具有吸收峰。对于全烷基环四硅烷3和4具有弯曲结构的光解会在293 K处发生光解，生成相应的亚甲硅烷基和环三硅烷，但在77 K的MP玻璃中则不会。这些光解作用源自激发单线态（S 1），这是由于瞬态吸收的快速建立而引起的跳动后。二异丙基甲硅烷基（S3）和叔丁基甲基甲硅烷基（S4）的瞬态峰分别在530和515 nm处观察到，寿命为38或50 ns。从其分子结构的角度讨论了环四硅烷的光化学反应。

  DOI：

  10.1039/f19898502369

文献信息

• A Combined Experimental and Theoretical Study of the Kinetics and Mechanism of the Addition of Alcohols to Electronically Stabilized Silenes:  A New Mechanism for the Addition of Alcohols to the SiC Bond
  作者：William J. Leigh、Thomas R. Owens、Michael Bendikov、Sanjio S. Zade、Yitzhak Apeloig

  DOI：10.1021/ja0613557

  日期：2006.8.1

  other silenes that have been studied previously. The data are consistent with a mechanism involving reaction with the hydrogen-bonded dimer of the alcohol, (MeOH)2 (k = 40 ± 3 M-1 s-1; kH/kD = 1.7 ± 0.2). The stable analogue of silene 4, 1-tert-butyldimethylsilyl-1-trimethylsilyl-2-adamantylidenesilane (5), reacts ∼50 times more slowly, but via the same mechanism. The mechanism for addition of water

  稳定的 silene 1,1-双（三甲基甲硅烷基）-2-金刚烷基硅烷 (4) 是通过一种新型三硅杂环丁烷衍生物在各种溶剂中的光解生成的，并通过动力学紫外分光光度法直接研究。由于头对头二聚作用，Silene 4 在 23 °C (k/e = 8.6 × 10-6 cm s-1) 的脱气己烷溶液中以二级动力学衰减。它与氧气快速反应 [k(25 °C) ≈ 3 × 105 M-1 s-1]，但与之前研究过的其他硅酮相比，甲醇 (MeOH) 反应慢约 10 个数量级。数据与涉及与醇的氢键二聚体 (MeOH)2 反应的机制一致（k = 40 ± 3 M-1 s-1；kH/kD = 1.7 ± 0.2）。silene 4 的稳定类似物 1-叔丁基二甲基甲硅烷基-1-三甲基甲硅烷基-2-金刚烷基硅烷 (5) 的反应速度要慢 50 倍左右，但反应机理相同。
• 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.
• Photolysis of cyclotetrasilanes. Remarkable dependence on molecular structure
  作者：Haruo Shizuka、Kazuyuki Murata、Yasushi Arai、Kenichi Tonokura、Hideaki Tanaka、Hideyuki Matsumoto、Yoichiro Nagai、Greg Gillette、Robert West

  DOI：10.1039/f19898502369

  日期：——

  at 415 nm at 77 K. For the peralkylcyclotetrasilanes 3 and 4 having bent structures, photolysis occurs to give the corresponding silylene and cyclotrisilane at 293 K, but not in MP glass at 77 K. These photolyses originate from the excited singlet state (S1), judging from a rapid build-up of the transient absorption after pulsing. Transient peaks for diisopropylsilylene (S3) and t-butylmethylsilylene

  环四硅烷的光解反应是通过在293 K的甲基环己烷（MCH）中进行激光闪光光解，以及在77 K的甲基环己烷-异戊烷（MP; 3：1，v / v）玻璃中进行稳态光解。关于环四硅烷的分子结构。平面的全甲硅烷基环四硅烷1和2生成相应的二硅酮（D1和D2），在293 K处的410 nm和77 K下的415 nm处具有吸收峰。对于全烷基环四硅烷3和4具有弯曲结构的光解会在293 K处发生光解，生成相应的亚甲硅烷基和环三硅烷，但在77 K的MP玻璃中则不会。这些光解作用源自激发单线态（S 1），这是由于瞬态吸收的快速建立而引起的跳动后。二异丙基甲硅烷基（S3）和叔丁基甲基甲硅烷基（S4）的瞬态峰分别在530和515 nm处观察到，寿命为38或50 ns。从其分子结构的角度讨论了环四硅烷的光化学反应。