(t-Bu2MeSi)2SiH2 | 461054-13-7

• 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: (t-Bu2MeSi)2SiH2
• 英文别名: bis(di-tert-butylmethylsilyl)silane
• CAS: 461054-13-7
• 化学式: C₁₈H₄₄Si₃
• 分子量: 344.804
• InChiKey: KFZAXSUVTNKDSD-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：

  (t-Bu2MeSi)2SiH2 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以96%的产率得到2,2-dibromo-1,1,3,3-tetra-tert-butyl-1,3-dimethyltrisilane
  参考文献：
  名称：

  缺乏与 π 键共轭的可分离甲硅烷基和 Germyl 自由基：合成、表征和反应性

  摘要：

  三[二-叔丁基（甲基）甲硅烷基]甲硅烷基和-甲硅烷基阴离子与二氯甲撑-二恶烷络合物的单电子氧化反应导致形成稳定的三[二-叔丁基（甲基）甲硅烷基]甲硅烷基和- Geryl 自由基 1 和 2，代表第 14 族较重元素的第一个可分离自由基物种，缺乏通过与 pi 键共轭的稳定性。甲硅烷基和锗基自由基 1 和 2 的晶体结构显示出围绕自由基中心的完全平面几何形状。由于与 29Si 和 73Ge 核的耦合，1 和 2 的 ESR 光谱显示出具有特征卫星的强信号。超精细耦合常数 a(29Si) 和 a(73Ge) 的小值清楚地表明两个自由基的 pi 特征，对应于自由基中心的平面几何形状和 sp2 杂化。

  DOI：

  10.1021/ja0126780
• 作为产物：
  描述：

  2,2-dibromo-1,1,3,3-tetra-tert-butyl-1,3-dimethyltrisilane 在 potassium graphite 、 氢气 作用下， 以 四氢呋喃 、 氘代苯 为溶剂， 反应 3.0h， 生成 (t-Bu2MeSi)2SiH2
  参考文献：
  名称：

  DMAP 稳定的双（甲硅烷基）甲硅烷基作为有机硅化合物的通用合成子

  摘要：

  DMAP 稳定的甲硅烷基 1a-c是在 DMAP 存在下通过相应二溴硅烷的还原脱溴获得的。讨论了它们通过C-H 键活化、脱芳环扩展和甲硅烷基迁移的明显不同的热异构化反应。此外，配合物1在高温下解离，原位提供相应的游离甲硅烷基，其甚至能够单点活化 H 2。此外，钾取代的以硅为中心的自由基2与( t Bu 3 Si) 2 SiBr 2的过度还原分离。

  DOI：

  10.1039/c9ra10628f

文献信息

• Mercury-Substituted Silyl Radical Intermediates in Formation and Fragmentation of Geminal Dimercury Silyl Compounds
  作者：Dmitry Bravo-Zhivotovskii、Ilya Ruderfer、Michael Yuzefovich、Monica Kosa、Mark Botoshansky、Boris Tumanskii、Yitzhak Apeloig

  DOI：10.1021/om050118u

  日期：2005.5.1

  The first known trimercury and cyclic tetramercury organosilicon compounds containing the −(Hg−R2Si−Hg)− fragment, (t-BuHgSiR2)2Hg [R = i-Pr3Si (3a), R = t-Bu2MeSi (3b)] and [(i-Pr3Si)2SiHg]4 (6), were synthesized and characterized. Reactions of the corresponding H2SiR2 silanes with t-Bu2Hg yielded 3a and 3b. 6 was obtained from a hexane solution of 3a that was stored at room temperature for 6 months

  含有-（Hg-R 2 Si-Hg）-片段（（t -BuHgSiR 2）2 Hg [R = i- Pr 3 Si（3a），R = t- Bu 2合成并表征了MeSi（3b）]和[（i- Pr 3 Si）2 SiHg] 4（6）。相应的H 2 SiR 2硅烷与t- Bu 2 Hg的反应生成3a和3b。从3a的己烷溶液中获得6，将其在室温下保存6个月。通过X射线分析确定3a，3b和6的分子结构。3的光解和热解导致形成汞取代的甲硅烷基（以前未知）。通过详细的EPR研究和捕获2,2,6,6，-四甲基-1-哌啶基氧基（TEMPO）自由基证实了它们的结构。通过在Hg-取代的甲硅烷基自由基的反应混合物中观察到EPR信号，证明了形成3的自由基机理。
• 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.
• Isolable Photoreactive Polysilyl Radicals
  作者：Gregory Molev、Boris Tumanskii、Dennis Sheberla、Mark Botoshansky、Dmitry Bravo-Zhivotovskii、Yitzhak Apeloig

  DOI：10.1021/ja905097b

  日期：2009.8.26

  Reaction of silyl substituted dichlorosilanes with lithiosilanes in hexane leads exclusively to the corresponding stable silyl radicals. Two radicals, the new (t-Bu2MeSi)(2)HSi(t-Bu2MeSi)(2)Si center dot (1) and the previously isolated (t-Bu2MeSi)(3)Si center dot (2), were isolated and fully characterized including by X-ray crystallography. This one-step method is general and was applied for the synthesis of other silyl. radicals. Upon irradiation radical 1 (yellow solution in hexane) decays to yield the corresponding disproportionation products, silane and disilene (blue colored). In contrast, radical 2 is photostable in the absence of additives, but it abstracts hydrogen from triethylsilane and 2-propanol upon irradiation. DFT calculations and irradiation experiments with lambda > 400 nm suggest that SOMO-1 square SOMO excitation, which provides better electron accepting properties to the radical, is responsible for the photoreactivity of 1 and 2.
• [{(tBu2Me)2Si}3Li4]2−: An Aggregated Dianion of a 1,1-Dilithiosilane with a Unique Structural Motif
  作者：Dmitry Bravo-Zhivotovskii、Ilya Ruderfer、Semyon Melamed、Mark Botoshansky、Asher Schmidt、Yitzhak Apeloig

  DOI：10.1002/anie.200600308

  日期：2006.6.19
• DMAP-stabilized bis(silyl)silylenes as versatile synthons for organosilicon compounds
  作者：Richard Holzner、Dominik Reiter、Philipp Frisch、Shigeyoshi Inoue

  DOI：10.1039/c9ra10628f

  日期：——

  silylenes 1a–c are obtained from the reductive debromination of the corresponding dibromosilanes in the presence of DMAP. Their distinctly different thermal isomerization reactions via C–H bond activation, dearomative ring expansion and silyl migration are discussed. Furthermore, complexes 1 dissociate at elevated temperatures, providing the corresponding free silylenes in situ, which are even capable

  DMAP 稳定的甲硅烷基 1a-c是在 DMAP 存在下通过相应二溴硅烷的还原脱溴获得的。讨论了它们通过C-H 键活化、脱芳环扩展和甲硅烷基迁移的明显不同的热异构化反应。此外，配合物1在高温下解离，原位提供相应的游离甲硅烷基，其甚至能够单点活化 H 2。此外，钾取代的以硅为中心的自由基2与( t Bu 3 Si) 2 SiBr 2的过度还原分离。