1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene | 321527-61-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene
• 英文别名: 1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopent-2,4-diene；1,1,2,3-(methyldi-tert-butylsilyl)-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene；[lithium 1,2,3-tris(di-tert-butylmethylsilyl)-4-phenyl-1,2-disila-3-germacyclopentadienide]*THF
• CAS: 321527-61-1
• 化学式: C₄₄H₉₀GeSi₆
• 分子量: 860.302
• InChiKey: JCZFETMLIVAIIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.79
• 重原子数：
  51.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene 在 KC₈ 作用下， 以 四氢呋喃 、 氘代四氢呋喃 为溶剂， 生成 (η1-1,1,2,3-(methyldi-tert-butylsilyl)-4-phenyl-1,2-disila-3-germacyclopenta-2,4-dienide)lithium
  参考文献：
  名称：

  The Heavy Analogue of CpLi:  Lithium 1,2-Disila-3-germacyclopentadienide, a 6π-Electron Aromatic System

  摘要：

  Lithium 1,2-disila-3-germacyclopentadienide 2-.Li+ was synthesized by the reduction of 1,2-disila-3-germacyclopenta-2,4-diene 1 with potassium graphite followed by treatment with an excess amount of LiBr. The X-ray analysis of 2-.[Li+(THF)] revealed a delocalized aromatic cyclopentadienide-type structure with the diagnostic eta5-coordination of the Li+ cation to the five-membered ring. Aromaticity of this compound was verified and confirmed by theoretical calculations. The solution behavior of the 2-.Li+ is different in nonpolar and polar solvents; in nonpolar toluene, 2-.Li+ maintained the properties of a delocalized aromatic compound with the characteristically shielded 7Li NMR resonance at -5.4 ppm, whereas in polar THF, 2-.Li+ exhibited the properties of a localized nonaromatic compound with the negative charge situated on the Ge atom.

  DOI：

  10.1021/ja054398g
• 作为产物：
  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

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。
• Unexpected Hydrolithiation of M=M′ Double Bond (M, M′ = Si, Ge) with<i>^t</i>BuLi
  作者：Vladimir Ya. Lee、Akira Sekiguchi

  DOI：10.1246/cl.2004.84

  日期：2004.2

  The reduction of 2- and 1-disilagermirenes 1 and 2 with tBuLi proceeded regio- and stereospecifically to produce germyllithium derivative 4—the product of the formal addition of LiH across the M=M′ bond (M, M′ = Si, Ge) through single electron transfer steps. Reduction of 1,2-disila-3-germacyclopenta-2,4-diene derivative 3 with tBuLi also proceeded specifically, but with an opposite regioselectivity to form silyllithium derivative 7.

  用叔丁基锂还原 2-和 1-二稀释锗烯 1 和 2 的过程具有区域和立体选择性，生成了锗锂衍生物 4--这是 LiH 通过单电子转移步骤在 M=M′ 键（M, M′ = Si, Ge）上正式加成的产物。用叔丁基锂还原 1,2-二拉-3-锗基环戊-2,4-二烯衍生物 3 时，也进行了特异性还原，但具有相反的区域选择性，生成了 silyllithium 衍生物 7。
• The First Metalladiene of Group 14 Elements with a Silole-Type Structure with SiGe and CC Double Bonds
  作者：Vladimir Ya. Lee、Masaaki Ichinohe、Akira Sekiguchi

  DOI：10.1021/ja0030921

  日期：2000.12.1
• 2,4-Disila-1-germatricyclo[2.1.0.0^2,5]pentane:  A New Type of Cage Compound of Group 14 Elements with an Extremely Long Ge−C Bridge Bond and an “Umbrella”-Type Configuration of a Ge Atom
  作者：Vladimir Ya. Lee、Masaaki Ichinohe、Akira Sekiguchi

  DOI：10.1021/ja020574z

  日期：2002.8.1

  The thermolysis of 1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene 1 at 175 degrees C results in the quantitative formation of 1,2,3,4-tetrakis[di-tert-butyl(methyl)silyl]-5-phenyl-2,4-disila-1-germatricyclo[2.1.0. 02,5]pentane 2, representing a new type of cage compound of group 14 elements. The crystal structure of 2 was established by X-ray crystallography, which showed an extremely long Ge-C bridge bond of 2.242(3) A and an "umbrella"-type configuration of the Ge atom. The compound 2 readily reacted with benzaldehyde to produce 1,4,5,7-tetrakis[di-tert-butyl(methyl)silyl]-3,6-diphenyl-2-oxa-1,4-disila-5-germabicyclo[2.2.1]hept-5-ene 3 with an endocyclic Ge=C double bond.