E-1,2-di[bis(trimethylsilyl)amino]-1,2-di(pentamethylcyclopentadienyl)disilene | 765317-10-0

• 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: E-1,2-di[bis(trimethylsilyl)amino]-1,2-di(pentamethylcyclopentadienyl)disilene
• 英文别名: E-[(Me3Si)2N](η1-Me5C5)Si=Si(η1-C5Me5)[N(SiMe3)2]；trans-1,2-bis[bis(trimethylsilyl)amino]-1,2-bis(pentamethylcyclopentadienyl)disilene；trans-[(TMS)2N(η1-Me5C5)Si=Si(η1-Me5C5)-N(TMS)2]；5-[(E)-[bis(trimethylsilyl)amino]-[[bis(trimethylsilyl)amino]-(1,2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl)silylidene]silyl]-1,2,3,4,5-pentamethylcyclopenta-1,3-diene
• CAS: 765317-10-0
• 化学式: C₃₂H₆₆N₂Si₆
• 分子量: 647.402
• InChiKey: YHWUPWBOFBAOMS-ULDVOPSXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.88
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  E-1,2-di[bis(trimethylsilyl)amino]-1,2-di(pentamethylcyclopentadienyl)disilene 在 sulfur 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以60%的产率得到
  参考文献：
  名称：

  Reactivity Studies of a Disilene with N₂O and Elemental Sulfur

  摘要：

  In a previous contribution, we have reported on a convenient and high yield synthesis of the disilene trans-[(TMS)(2)N(eta(1)-Me5C5)-Si=Si(eta(1)-Me5C5)N(TMS)(2)] (2). Herein, we show the reactions of 2 with N2O and S-g. The former reaction affords two isomeric (cis- and trans-) dioxadisiletane ring compounds. To the best of our knowledge, this is the first report where both cis- and trans-isomers are isolated from the same disilene precursor and characterized structurally by single-crystal X-ray diffraction (XRD) studies. The reaction of 2 with elemental sulfur yields only the trans-isomer. To investigate this dissimilar reaction pattern exhibited by 2, computational studies were performed. Density functional theory (DFT) calculations showed that the two dioxadisiletane ring isomers are isoenergetic, with the trans isomer being slightly more stable than the cis counterpart, by 3.3 kcal/mol, while that is not the case with sulfur. All the isolated compounds are characterized by single-crystal XRD studies, multinuclear NMR spectroscopy, and electron ionization mass spectrometry (EI-MS).

  DOI：

  10.1021/ic201419m
• 作为产物：
  描述：

  [bis(trimethylsilyl)amino](pentamethylcyclopentadienyl)silicon(II) 以 正己烷 为溶剂， 反应 240.0h， 以25%的产率得到E-1,2-di[bis(trimethylsilyl)amino]-1,2-di(pentamethylcyclopentadienyl)disilene
  参考文献：
  名称：

  通过相转移将稳定的单体硅 (II) 化合物可逆地转化为稳定的二硅烷：系统 {[(Me3Si)2N](Me5C5)Si }nwithn= 1,2 的实验和理论研究

  摘要：

  盐（eta（5）-五甲基环戊二烯基）硅（II）四（五氟苯基）硼酸盐（5）在-78℃下与双（三甲基甲硅烷基）氨基锂在二甲氧基乙烷（DME）作为溶剂反应，定量得到化合物[双（三甲基甲硅烷基）氨基][五甲基环戊二烯基]硅（II）6A，呈无色粘稠油状。在 -40 摄氏度进行的反应生成硅 (IV) 化合物 7，即 6A 与 DME 的正式氧化加成产物。在 6A 与 2,3-二甲基丁二烯的反应中观察到环加成反应，得到硅 (IV) 化合物 8。 在尝试从有机溶剂如己烷、THF 或甲苯中结晶 6A 时，深黄色化合物 trans-1,2 -双[双（三甲基甲硅烷基）氨基]-1,2-双（五甲基环戊二烯基）二硅烯（6B），6A的形式二聚体，从无色溶液中结晶，但只有在几天甚至几周之后。在尝试将二硅烷 6B 溶解在所述有机溶剂中时，在长时间剧烈摇动或超声处理后获得无色溶液。在溶剂蒸发后，可以从该溶液中回收纯 6A。这个转换过程可以重复多次。在

  DOI：

  10.1021/ja902153u

文献信息

• One Pot Synthesis of Disilatricycloheptene Analogue and Jutzi’s Disilene
  作者：Shabana Khan、Sakya S. Sen、Herbert W. Roesky、Daniel Kratzert、Reent Michel、Dietmar Stalke

  DOI：10.1021/ic101552r

  日期：2010.10.18

  The reaction of LiN(TMS)(2) (TMS = Me3Si) with dichlorosilane (Me5C5)SiHCl2 (1) in a molar ratio of 3:2 at ambient temperature leads to the formation of the disilatricycloheptene analogue (2). Compound 2 consists of three (three-, four-, and five-membered) fused rings that together form a six-membered heterocyclic ring. However, the reaction of 1 with KN(TMS)(2) affords the formation of disilene of composition E-[(TMS)(2)N](eta(1)-Me5C5)Si=Si(eta(1)-Me5C5)[N(TMS)(2)] (3) in good yield. This is a convenient and facile route for the synthesis of 3 in a single step and supports the formation of (Me(5)c(5))SiN(TMS)(2) as an intermediate.
• Reversible Transformation of a Stable Monomeric Silicon(II) Compound into a Stable Disilene by Phase Transfer: Experimental and Theoretical Studies of the System {[(Me₃Si)₂N](Me₅C₅)Si }_<i>n</i> with <i>n</i> = 1,2
  作者：Peter Jutzi、Andreas Mix、Beate Neumann、Britta Rummel、Wolfgang W. Schoeller、Hans-Georg Stammler、A. B. Rozhenko

  DOI：10.1021/ja902153u

  日期：2009.9.2

  icon(II) tetrakis(pentafluorophenyl)borate (5) reacts at -78 degrees C with lithium bis(trimethylsilyl)amide in dimethoxyethane (DME) as solvent to give quantitatively the compound [bis(trimethylsilyl)amino][pentamethylcyclopentadienyl]silicon(II) 6A in the form of a colorless viscous oil. The reaction performed at -40 degrees C leads to the silicon(IV) compound 7, the formal oxidative addition product

  盐（eta（5）-五甲基环戊二烯基）硅（II）四（五氟苯基）硼酸盐（5）在-78℃下与双（三甲基甲硅烷基）氨基锂在二甲氧基乙烷（DME）作为溶剂反应，定量得到化合物[双（三甲基甲硅烷基）氨基][五甲基环戊二烯基]硅（II）6A，呈无色粘稠油状。在 -40 摄氏度进行的反应生成硅 (IV) 化合物 7，即 6A 与 DME 的正式氧化加成产物。在 6A 与 2,3-二甲基丁二烯的反应中观察到环加成反应，得到硅 (IV) 化合物 8。 在尝试从有机溶剂如己烷、THF 或甲苯中结晶 6A 时，深黄色化合物 trans-1,2 -双[双（三甲基甲硅烷基）氨基]-1,2-双（五甲基环戊二烯基）二硅烯（6B），6A的形式二聚体，从无色溶液中结晶，但只有在几天甚至几周之后。在尝试将二硅烷 6B 溶解在所述有机溶剂中时，在长时间剧烈摇动或超声处理后获得无色溶液。在溶剂蒸发后，可以从该溶液中回收纯 6A。这个转换过程可以重复多次。在
• Reactivity Studies of a Disilene with N₂O and Elemental Sulfur
  作者：Shabana Khan、Reent Michel、Debasis Koley、Herbert W. Roesky、Dietmar Stalke

  DOI：10.1021/ic201419m

  日期：2011.11.7

  In a previous contribution, we have reported on a convenient and high yield synthesis of the disilene trans-[(TMS)(2)N(eta(1)-Me5C5)-Si=Si(eta(1)-Me5C5)N(TMS)(2)] (2). Herein, we show the reactions of 2 with N2O and S-g. The former reaction affords two isomeric (cis- and trans-) dioxadisiletane ring compounds. To the best of our knowledge, this is the first report where both cis- and trans-isomers are isolated from the same disilene precursor and characterized structurally by single-crystal X-ray diffraction (XRD) studies. The reaction of 2 with elemental sulfur yields only the trans-isomer. To investigate this dissimilar reaction pattern exhibited by 2, computational studies were performed. Density functional theory (DFT) calculations showed that the two dioxadisiletane ring isomers are isoenergetic, with the trans isomer being slightly more stable than the cis counterpart, by 3.3 kcal/mol, while that is not the case with sulfur. All the isolated compounds are characterized by single-crystal XRD studies, multinuclear NMR spectroscopy, and electron ionization mass spectrometry (EI-MS).