dichloro-bis[di-tert-butyl(methyl)silyl]germane | 303030-97-9

• 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: dichloro-bis[di-tert-butyl(methyl)silyl]germane
• 英文别名: dichlorobis(di-tert-butyl(methyl)silyl)germane；dichlorobis[di-tert-butyl(methyl)silyl]germane；bis(di-tert-butylmethylsilyl)dichlorogermane
• CAS: 303030-97-9
• 化学式: C₁₈H₄₂Cl₂GeSi₂
• 分子量: 458.198
• InChiKey: KJUKCRGRKFYWMU-UHFFFAOYSA-N

物化性质

• 沸点：
  374.6±25.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.42
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• 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：

  dichloro-bis[di-tert-butyl(methyl)silyl]germane 在 KC₈ 作用下， 以 四氢呋喃 为溶剂， 以91%的产率得到tetrakis(di-tert-butylmethylsilyl)digermirene
  参考文献：
  名称：

  A blue digermene (t-Bu2MeSi)2GeGe(SiMet-Bu2)2

  摘要：

  一种新颖的四(三烷基硅基)二锗烯，以其颇为独特的结构和化学性质而著称，通过一个直接的合成方法被合成出来：使用石墨化钾还原相应的二氯双(三烷基硅基)锗前驱体。

  DOI：

  10.1039/c0cc05415a
• 作为产物：
  描述：

  盐酸 、 [(tert-butyl)2Si(methyl)]2Ge(p-tolyl)2 在 三氯化铝 作用下， 以 苯 为溶剂， 以99%的产率得到dichloro-bis[di-tert-butyl(methyl)silyl]germane
  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

• The First Isolable 1,1-Dilithiogermane and Its Unusual Dimeric Structure-An Effective Reagent for the Preparation of Double-Bonded Derivatives of Group 14 Elements
  作者：Akira Sekiguchi、Rika Izumi、Shinji Ihara、Masaaki Ichinohe、Vladimir Ya. Lee

  DOI：10.1002/1521-3773(20020503)41:9<1598::aid-anie1598>3.0.co;2-8

  日期：2002.5.3
• The First Three-Membered Unsaturated Rings Consisting of Different Heavier Group 14 Elements:  1-Disilagermirene with a SiSi Double Bond and Its Isomerization to a 2-Disilagermirene with a SiGe Double Bond
  作者：Vladimir Ya. Lee、Masaaki Ichinohe、Akira Sekiguchi、Nozomi Takagi、Shigeru Nagase

  DOI：10.1021/ja001551s

  日期：2000.9.1
• Electronic Structure of Bis(silyl)carbon-, Bis(silyl)silicon-, and Bis(silyl)germanium-Centered Radicals (R₃Si)₂XE^• (E = C, Si, Ge; X = H, Re(CO)₅, F): EPR and DFT Studies
  作者：Dennis Sheberla、Boris Tumanskii、Dmitry Bravo-Zhivotovskii、Gregory Molev、Victoria Molev、Vladimir Ya. Lee、Kazunori Takanashi、Akira Sekiguchi、Yitzhak Apeloig

  DOI：10.1021/om100812b

  日期：2010.11.8

  Group 14 element bis(silyl)-substituted radicals (R3Si)(2)XE center dot(E = C, Si, Ge; X = Re(CO)(5), F) and (R3Si)(1-Ad)HC center dot have been studied by EPR spectroscopy and Dry calculations. The significant difference in the kinetic stability at 240 K of the hydrogen-substituted persistent C-centered and analogous short-lived Si- and Ge-centered radicals is explained by different decay mechanisms: H abstraction for E = C and dimerization for E = Si, Ge. The H-1(alpha) and Si-29(beta) hyperfine coupling constants (hfcc) in these radicals have dominating negative spin-polarization (SP) contribution; thus, they have a negative sign. In contrast, in the E-substituted radical, where a(F) results from spin delocalization and positive SP contribution, it has a positive sign. For Si-centered radicals it has been shown by calculations that the H-1(alpha) and Si-29(beta) hfcc's result from a combination of direct and spin-polarization mechanisms, which vary as a function of the degree of pyramidality around F. As the geometry around E changes from planar to pyramidal, the contribution of the direct mechanism increases and the contribution of spin polarization decreases. The hydrogen-substituted C radicals are planar (Sigma theta(C) = 360.0 degrees), in contrast to the analogous Si and Ge radicals, which are slightly pyramidal (Sigma theta(Si) = 354.1 degrees and Sigma theta(Ge) = 355.5 degrees). Both (R3Si)(2)XE center dot species (E = Si, Ge; X = Re(CO)(5)) are planar around E.