1,2,3,3-tetrakis[di-tert-butyl(methyl)silyl]-1-disilagermirene | 303030-98-0

• 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: 1,2,3,3-tetrakis[di-tert-butyl(methyl)silyl]-1-disilagermirene
• 英文别名: tetrakis(di-tert-butylmethylsilyl)-3H-disilagermirene；tetrakis[di-tert-butyl(methyl)-silyl]-1-disilagermirene
• CAS: 303030-98-0
• 化学式: C₃₆H₈₄GeSi₆
• 分子量: 758.166
• InChiKey: FJGWNMONCXLCMF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.7
• 重原子数：
  43.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1,2,3,3-tetrakis[di-tert-butyl(methyl)silyl]-1-disilagermirene 以 氘代苯 为溶剂， 生成 1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene
  参考文献：
  名称：

  Reaction of disilagermirenes with phenylacetylene: from a germasilene GeSi to a metalladiene of the type SiGeCC

  摘要：

  The reaction of tetrakis[di-tert-butyl(methyl)silyl]-2-disilagermirene (1b) with phenylacetylene at room temperature produced highly air- and moisture-sensitive bright orange crystals of 1, 1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene (2b), which represents a previously unknown metalladiene with one Si=Ge and one C=C double bond. The crystal structure of 2b was determined by X-ray crystallography, which showed a trans-bent configuration around the Si=Ge double bond with a bond length of 2.250(1) Angstrom. The reaction mechanism to form 2b, the question of conjugation of the two double bonds in a cyclopentadiene ring of 2b, as well as its reactivity are discussed. The reaction of tetrakis[di-tert-butyl(methyl)silyl]-1-disilagermirene (1a), which is an isomer of 1b, with phenylacetylene is also examined. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)00807-5
• 作为产物：
  描述：

  [(tert-butyl)2Si(methyl)]2Ge(p-tolyl)2 在 三氯化铝 sodium 作用下， 以 甲苯 、 苯 为溶剂， 生成 1,2,3,3-tetrakis[di-tert-butyl(methyl)silyl]-1-disilagermirene
  参考文献：
  名称：

  Disilagermirenes: heavy cyclopropenes of Si and Ge atoms

  摘要：

  Tetrakis[di-tert-butyl(methyl)silyl]-1-disilagermirene (3) was prepared by the reaction of 2,2,2-tribromo-1,1-di-tert-butyl-1-methyldisilane and dichlorobis[di-tert-butyl(methyl)silyl]germane with sodium in toluene. The molecular structure of 3 was established by X-ray crystallography, which showed a trans-bent configuration around the Si=Si double bond with a bond length of 2.146(1) Angstrom. Thermal and photochemical isomerization of 3 to tetrakis[di-tert-butyl(methyl)silyl]-2-disilagermirene (4) is also reported, as well as the reactions of 3 with MeI, PhCH2OH, and PhCOCH3. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(03)00651-x

文献信息

• Heavy analogues of the 6π-electron anionic ring systems: Cyclopentadienide ion and cyclobutadiene dianion
  作者：Vladimir Ya. Lee、Kazunori Takanashi、Risa Kato、Tadahiro Matsuno、Masaaki Ichinohe、Akira Sekiguchi

  DOI：10.1016/j.jorganchem.2007.01.011

  日期：2007.6

  4-digerma- and 1,2,3,4-tetrasilacyclobutadiene dianions 72− · 2[K+(thf)2] and 82− · 2[K+(thf)2], were synthesized by the reduction of the neutral precursors 1, 3 and 4, respectively. 2− · [Li+(thf)], the heavy analogue of the cyclopentadienide ion, is an aromatic compound, whereas 72− · 2[K+(thf)2] and 82− · 2[K+(thf)2], the heavy analogues of the cyclobutadiene dianion, are both non-aromatic.

  阴离子6π电子体系的重类似物，锂1,2-二硅杂-3- germacyclopentadienide 2 -  ·  [李+（THF）]，1,2-二硅杂-3,4- digerma-和1,2,3- ，4- tetrasilacyclobutadiene二价阴离子7 2 -  ·  2 [K +（THF）2 ]和8 2 -  ·  2 [K +（THF）2 ]中，通过中性前体的还原合成的1，3和4分别。2 −  ·  [Li +（thf）]中，环戊二烯离子的重类似物，是一种芳族化合物，而7 2 -  ·  2 [K +（THF）2 ]和8 2 -  ·  2 [K +（THF）2 ]中，环丁二烯二价阴离子的重类似物，都是非芳香族的。
• ——
  作者：Vladimir Ya. Lee、Masaaki Ichinohe、Akira Sekiguchi

  DOI：10.1039/b106801f

  日期：2001.10.11

  The 3H-disilagermirene, (tBu2MeSi)4GeSi2, reacts with alpha-hydrogen containing carbonyl compounds (acetophenone, butane-2,3-dione) by an 'ene'-reaction pathway followed by isomerization or insertion reactions, representing a new mode in the reaction of disilenes with carbonyl compounds.

  3H-二硅杂mir烯（tBu2MeSi）4GeSi2与含α-氢的羰基化合物（苯乙酮，2,3-丁烷丁二酮）通过``烯''反应途径反应，随后发生异构化或插入反应，这代表了一种新的模式二烯与羰基化合物的反应。
• ³Δ-1,2,3,4-Disilagermastannetene: the first cyclic germastannene
  作者：V. Ya. Lee、K. Takanashi、M. Nakamoto、A. Sekiguchi

  DOI：10.1023/b:rucb.0000041306.36397.62

  日期：2004.5

  (3)Delta-1,2,3,4-Disilagermastannetene, the first cyclic germastannene, was quantitatively synthesized by the reaction of 1- and 2-disilagermirenes with the dichlorostannylene-dioxane complex in THF. The title germastannene is quite stable in the solution, which was explained by the appreciable pi(Ge=Sn)-sigma*(Si-Cl) orbitals mixing.

  （3）δ-1,2,3,4-二硅基germastannene，首个环状germastannene，通过1-和2-二硅基germirene与二氯基 tinylene-二氧杂环己烷复合物在四氢呋喃中的反应定量合成。标题中的germastannene在溶液中非常稳定，这可归因于显著的π(Ge=Sn)-σ*(Si-Cl)轨道混杂作用。
• Reaction of 1-Disilagermirene with Benzaldehyde: An Unexpected Combination of Cycloaddition and Insertion Pathways
  作者：Vladimir Ya. Lee、Masaaki Ichinohe、Akira Sekiguchi

  DOI：10.1246/cl.2001.728

  日期：2001.7

  New strained bicyclic compounds were formed by the reaction of tetrakis[di-tert-butyl(methyl)silyl]-1-disilagermirene 1 with benzaldehyde, involving cycloaddition following the rearrangement and insertion pathways. Reaction of 1 with PhCHO gave three different products: two mono-adducts 2, 3 and one bis-adduct 4, depending on the ratio of the reagents and the reaction conditions.

  新的应变双环化合物是由四[二叔丁基（甲基）甲硅烷基]-1-二硅芴烯 1 与苯甲醛反应形成的，涉及重排和插入途径后的环加成反应。1 与 PhCHO 反应产生三种不同的产物：两种单加合物 2、3 和一种双加合物 4，这取决于试剂的比例和反应条件。
• A Chemical Trick:  How To Make a Digermene from a Disilene, Formation of ³Δ-1,2,3,4-Disiladigermetene
  作者：Vladimir Ya. Lee、Kazunori Takanashi、Masaaki Ichinohe、Akira Sekiguchi

  DOI：10.1021/ja021480s

  日期：2003.5.1

  hyl)silyl]-3Delta-1,2,3,4-disiladigermetene, 2, representing the first cyclotetrametallene containing two different heavier group 14 elements and the first digermene incorporated in a four-membered ring. trans-1,2-Dichloro-1,2,3,4-tetrakis[di-tert-butyl(methyl)silyl]-3Delta-1,2,3,4-disilagermastannetene (8), with a Ge=Sn double bond, was also prepared by the reaction of 1 with SnCl2.dioxane. The crystal

  四[二-叔丁基（甲基）甲硅烷基]二硅芴烯（1a 和 1b）与 GeCl2.二恶烷的意外反应导致反式-1,2-二氯-1,2,3,4-四烷[二叔丁基（甲基）甲硅烷基]-3Delta-1,2,3,4-二硅二甲烯，2，代表第一个环四金属烯，包含两个不同的较重的 14 族元素，第一个二甲烯包含在四元环中。trans-1,2-Dichloro-1,2,3,4-tetrakis[di-tert-butyl(methyl)silyl]-3Delta-1,2,3,4-disilagermastannetene (8), 与 Ge=Sn 双键，也由 1 与 SnCl2.二恶烷反应制备。2 的晶体结构是通过 X 射线晶体学建立的，其显示折叠的四元环骨架具有长 Ge=Ge 双键 (2.2911(4) A)。2的结构特点，以及其形成的可能机制，