(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