1,1,2,2-tetrakis(trimethylsilyl)dispiro[3,3',4,4'-biadamantane-1,2-disilacyclobutane] | 141397-68-4

• 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)dispiro[3,3',4,4'-biadamantane-1,2-disilacyclobutane]
• CAS: 141397-68-4
• 化学式: C₃₂H₆₄Si₆
• 分子量: 617.373
• InChiKey: BSLKYXHLZARJSB-UHFFFAOYSA-N

物化性质

• 密度：
  0.96±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.04
• 重原子数：
  38
• 可旋转键数：
  4
• 环数：
  9.0
• 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：

  苯乙烯 、 1,1,2,2-tetrakis(trimethylsilyl)dispiro[3,3',4,4'-biadamantane-1,2-disilacyclobutane] 以 正己烷 为溶剂， 反应 24.0h， 以87%的产率得到1,1-bis(trimethylsilyl)-3-phenylspiro(2,2-adamantane-1-silacyclobutane)
  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：

  1,1-bis(trimethylsilyl)-2-adamantylidenesilane 以 正己烷 为溶剂， 生成 1,1,2,2-tetrakis(trimethylsilyl)dispiro[3,3',4,4'-biadamantane-1,2-disilacyclobutane]
  参考文献：
  名称：

  醇加成电子稳定的 Silenes 的动力学和机理的联合实验和理论研究：一种将醇加成到 SiC 键的新机制

  摘要：

  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。

  DOI：

  10.1021/ja0613557

文献信息

• Vlaar, Mark J. M.; Ehlers, Andreas W.; Kanter, Frans J. J. de, Angewandte Chemie - International Edition, 2000, vol. 39, p. 4127 - 4130
  作者：Vlaar, Mark J. M.、Ehlers, Andreas W.、Kanter, Frans J. J. de、Schakel, Marius、Spek, Anthony L.、et al.

  DOI：——

  日期：——
• The Direct Synthesis of a Silene–Organometallic Complex
  作者：Dmitry Bravo-Zhivotovskii、Hanan Peleg-Vasserman、Monica Kosa、Gregory Molev、Mark Botoshanskii、Yitzhak Apeloig

  DOI：10.1002/anie.200353048

  日期：2004.1.30
• 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.
• 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。