1-tert-Butoxy-2-hydrotetramethyldisilane | 137938-35-3

• 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: 1-tert-Butoxy-2-hydrotetramethyldisilane
• 英文别名: 1-(tert-butyloxy)dimethyl-2-dimethyldisilane；HSiMe2SiMe2O-t-Bu；1-tert-Butoxy-1,1,2,2-tetramethyldisilane；dimethylsilyl-dimethyl-[(2-methylpropan-2-yl)oxy]silane
• CAS: 137938-35-3
• 化学式: C₈H₂₂OSi₂
• 分子量: 190.433
• InChiKey: NNTWCVJAKHGYLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.57
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Ru-{κ²(Si,Si)xantsil}(CO)(η⁶-toluene) 、 1-tert-Butoxy-2-hydrotetramethyldisilane 以 二氯甲烷 为溶剂， 以84%的产率得到Ru(κ3(O,Si,Si)-(9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)))(CO)(H)(SiMe2O(t-Bu)SiMe2)
  参考文献：
  名称：

  Synthesis, structure, and reactivity of hydridobis(silylene)ruthenium(IV)-xantsil complexes (xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)) — A stabilized form of key intermediates in the catalytic oligomerization–deoligomerization of hydrosilanes

  摘要：

  已发现 Ru{κ²(Si,Si)-xantsil}(CO)(η⁶-C₆H₅CH₃) (1) 是 HSiMe₂SiMe₃ 的寡聚-去聚合催化剂，在90°C处理2天后生成 H(SiMe₂)_nMe (n = 1–8)。将1与HSiMe₂SiMe₂OR (R = Me, t-Bu) 反应，可定量生成 Ru{κ³(O,Si,Si)-xantsil}(CO)(H){(SiMe₂•••O(R)•••SiMe₂)} (R = Me (2a), t-Bu (2b))，也可作为 HSiMe₂SiMe₃ 的寡聚-去聚合催化剂。基于这些实验结果，提出了涉及硅烷(硅烯)中间体的寡聚-去聚合机理。在甲苯-d₈中，2a 与 MeOH 反应生成 Ru{κ²(Si,Si)-xantsil}(CO)(η⁶-甲苯-d₈) 和 Me₂Si(OMe)₂，伴随释放 H₂。在 CO 气氛下，2a 顺利转化为其 CO 加合物 Ru{κ²(Si,Si)-xantsil}(CO)₂(H){(SiMe₂•••O(Me)•••SiMe₂)} (3)。关键词：硅烯配合物、钌、聚硅烷、脱氢偶联、寡聚合。

  DOI：

  10.1139/v03-151
• 作为产物：
  描述：

  1-chloro-2-hydro-1,1,2,2-tetramethyldisilane 、 叔丁醇 在 三乙胺 作用下， 反应 36.0h， 以72%的产率得到1-tert-Butoxy-2-hydrotetramethyldisilane
  参考文献：
  名称：

  Semenov, V. V.; Ladilina, E. Yu.; Chesnokova, T. A., Journal of general chemistry of the USSR, 1991, vol. 61, # 5.2, p. 1077 - 1086

  摘要：

  DOI：

文献信息

• Coordinatively Unsaturated Ru(II) Species Ru(xantsil)(CO): A New Active Catalyst for Oligomerization/Deoligomerization of HSiMe₂SiMe₃[xantsil=(9,9-Dimethylxanthene-4,5-diyl)bis(dimethylsilyl)]. Isolation of a Stabilized Form of the Silyl(silylene) Intermediates
  作者：Jim Josephus G. Minglana、Masaaki Okazaki、Hiromi Tobita、Hiroshi Ogino

  DOI：10.1246/cl.2002.406

  日期：2002.3

  Ru(xantsil)(CO)(η6-C6H5CH3) (1) was found to be a catalyst for the oligomerization/deoligomerization of HSiMe2SiMe3 to give H(SiMe2)nMe (n=1–8). A possible mechanism involving a silyl(silylene) intermediate was strongly supported by the isolation of its stabilized form, i.e., alkoxy-bridged bis(silylene) complex which was characterized by X-ray crystal structure analysis.

  Ru(xantsil)(CO)(η6-C6H5CH3) (1) 被发现是一种催化剂，用于 HSiMe2SiMe3 的低聚合/解聚反应，生成 H(SiMe2)nMe (n=1–8)。一种涉及硅烯（silylene）中间体的可能机制得到了强有力的支持，因为其稳定形式，即通过醇氧桥连的双（硅烯）络合物被分离出来，并通过X射线晶体结构分析进行了表征。
• Fluxional Behavior of Alkoxy-Bridged Bis(silylene)ruthenium Complexes Cp^*(Me₃P)Ru{SiMe₂···O(R)···SiMe₂}(R = Me,^tBu) Caused by Rotation of the Silylene Ligands
  作者：Hiroaki Wada、Hiromi Tobita、Hiroshi Ogino

  DOI：10.1246/cl.1998.993

  日期：1998.10

  The exchange of Si-Me groups caused by silylene ligand rotation in alkoxy-bridged bis(silylene)complexes Cp*(Me3P)RuSiMe2···O(R)···SiMe2}(R = Me,tBu) is observed by the variable temperature 1H NMR (VT 1H NMR) spectroscopy. This fluxionality is considered to be due to the weakened Si···O partial bonds caused by the strong electron-releasing effect of Cp* and PMe3 ligands.

  通过可变温度1H NMR（VT 1H NMR）光谱观察到烷氧基桥联双（硅烯）络合物Cp*(Me3P)RuSiMe2···O(R)···SiMe2}(R = Me,tBu)中硅-甲基基团因硅烯配体旋转而发生交换。这种可变性被认为是由于Cp*和PMe3配体的强电子释放效应导致Si···O部分键的弱化。
• Synthesis, structure, and reactivity of hydridobis(silylene)ruthenium(IV)-xantsil complexes (xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)) — A stabilized form of key intermediates in the catalytic oligomerization–deoligomerization of hydrosilanes
  作者：Masaaki Okazaki、Jim Josephus Gabrillo Minglana、Nobukazu Yamahira、Hiromi Tobita、Hiroshi Ogino

  DOI：10.1139/v03-151

  日期：2003.11.1

  Ruκ²(Si,Si)-xantsil}(CO)(η⁶-C₆H₅CH₃) (1) was found to be a catalyst for oligomerization–deoligomerization of HSiMe₂SiMe₃ to give H(SiMe₂)_nMe (n = 1–8 at 90 °C for 2 days). Treatment of 1 with HSiMe₂SiMe₂OR (R = Me, t-Bu) led to quantitative formation of Ruκ³(O,Si,Si)-xantsil}(CO)(H)(SiMe₂•••O(R)•••SiMe₂)} (R = Me (2a), t-Bu (2b)), which also worked as a catalyst for oligomerization–deoligomerization of HSiMe₂SiMe₃. Based on these experimental results, a mechanism involving silyl(silylene) intermediates was proposed for the oligomerization–deoligomerization of HSiMe₂SiMe₃. Complex 2a reacted with MeOH in toluene-d₈ to give Ruκ²(Si,Si)-xantsil}(CO)(η⁶-toluene-d₈) and Me₂Si(OMe)₂ with evolution of H₂. Under a CO atmosphere, 2a was smoothly converted to its CO adduct Ruκ²(Si,Si)-xantsil}(CO)₂(H)(SiMe₂•••O(Me)•••SiMe₂)} (3).Key words: silylene complex, ruthenium, polysilane, dehydrogenative coupling, oligomerization.

  已发现 Ruκ²(Si,Si)-xantsil}(CO)(η⁶-C₆H₅CH₃) (1) 是 HSiMe₂SiMe₃ 的寡聚-去聚合催化剂，在90°C处理2天后生成 H(SiMe₂)_nMe (n = 1–8)。将1与HSiMe₂SiMe₂OR (R = Me, t-Bu) 反应，可定量生成 Ruκ³(O,Si,Si)-xantsil}(CO)(H)(SiMe₂•••O(R)•••SiMe₂)} (R = Me (2a), t-Bu (2b))，也可作为 HSiMe₂SiMe₃ 的寡聚-去聚合催化剂。基于这些实验结果，提出了涉及硅烷(硅烯)中间体的寡聚-去聚合机理。在甲苯-d₈中，2a 与 MeOH 反应生成 Ruκ²(Si,Si)-xantsil}(CO)(η⁶-甲苯-d₈) 和 Me₂Si(OMe)₂，伴随释放 H₂。在 CO 气氛下，2a 顺利转化为其 CO 加合物 Ruκ²(Si,Si)-xantsil}(CO)₂(H)(SiMe₂•••O(Me)•••SiMe₂)} (3)。关键词：硅烯配合物、钌、聚硅烷、脱氢偶联、寡聚合。

• Semenov, V. V.; Ladilina, E. Yu.; Chesnokova, T. A., Journal of general chemistry of the USSR, 1991, vol. 61, # 5.2, p. 1077 - 1086
  作者：Semenov, V. V.、Ladilina, E. Yu.、Chesnokova, T. A.、Cherepennikova, N. F.

  DOI：——

  日期：——