bis(di-tert-butylmethylsilyl)germane | 1253975-92-6

• 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: bis(di-tert-butylmethylsilyl)germane
• CAS: 1253975-92-6
• 化学式: C₁₈H₄₄GeSi₂
• 分子量: 389.308
• InChiKey: VRMFSDRGXXXBBA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.51
• 重原子数：
  21.0
• 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：

  bis(di-tert-butylmethylsilyl)germane 以 四氢呋喃 为溶剂， 反应 20.58h， 生成
  参考文献：
  名称：

  真正的甲锗烷锂和第一个持久甲锗烷自由基的合成

  摘要：

  合成了两种新型锗基锂（ 1a和2b ），它们具有真正的C=Ge键和具有温和电子效应的取代基，并进行了结构表征。化合物1a （或2b ）的进一步氧化产生第一个持久的甲锗烷基自由基13a （或13b ） ，其通过EPR光谱和DFT计算进行表征。

  DOI：

  10.1002/anie.202202452
• 作为产物：
  描述：

  dichloro-bis[di-tert-butyl(methyl)silyl]germane 、 lithium aluminium tetrahydride 以 乙醚 为溶剂， 以66%的产率得到bis(di-tert-butylmethylsilyl)germane
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/om100812b

文献信息

• A High Yield Synthesis of an Octastannacubane and a Bis(silyl) Stannylene via Reductive Elimination of a Silane
  作者：Roman Bashkurov、Yosi Kratish、Natalia Fridman、Dmitry Bravo‐Zhivotovskii、Yitzhak Apeloig

  DOI：10.1002/anie.202013007

  日期：2021.2.8

  along with tBu2MeSiH. Octastannacubane 9 was characterized by X‐ray crystallography, NMR and UV/Vis spectroscopy. Based on DFT quantum‐mechanical calculations the 11 → 9 transformation occurs via reductive elimination of two tBu2MeSiH molecules from 11 yielding a distannyne, (or its bis‐stannylene isomer), followed by its tetramerization.

  三（甲硅烷基）氢化锡2在70°C的温度下热解3小时，从而消除了tBu 2 MeSiH，并生成了双（甲硅烷基）亚锡3，该二聚甲硅烷基可瞬间二聚得到二苯乙烯4。化合物3可以被NHC Me截留，生成亚苯乙烯-NHC Me络合物5。在加热（70°C，24小时）4时，生成锡烷基自由基8以及戊烷三环[2.1.0.0 2，5 ]戊烷10（约30％）和痕量（约5％）新型十八烷9。值得注意的是，octastannacubane 9通过适度加热（50°C）1,1,2,2-四甲硅烷基二锡烷11与tBu 2 MeSiH可以70％的产率生产。Octastannacubane 9的特征在于X射线晶体学，NMR和UV / Vis光谱。基于DFT的量子力学的计算的11 → 9经由两个TBU的还原消除发生转变2从MeSiH分子11产生一个distannyne，（或它的双-异构体stannylene），其次是它的四聚。
• Facile Synthesis of an Octagermacubane with Two Three‐Coordinate Germanium(0) Atoms and its Unique Radical Anion
  作者：Roman Bashkurov、Alexander Kaushansky、Boris Tumanskii、Natalia Fridman、Dmitry Bravo‐Zhivotovskii、Yitzhak Apeloig

  DOI：10.1002/anie.202300847

  日期：——

  an octagermacubane, having two 3-coordinate Ge0 atoms, by the thermolysis of a 1 : 1 mixture of tris(silyl)germane and bis(silyl)germane at 100 °C, is reported. Reduction of the octagermacubane with tBuMe2SiNa yields the first X-ray crystallography structure of a Ge-centered octagermacubane radical anion.

  据报道，通过在 100 °C 下热解三（甲硅烷基）锗烷和双（甲硅烷基）锗烷的 1:1 混合物，可以轻松合成具有两个 3 配位 Ge 0 原子的八锗立方烷。用tBuMe 2 SiNa还原octagermacubane产生了第一个以Ge 为中心的octagermacubane 自由基阴离子的X 射线晶体结构。