Bis[4-(trifluoromethyl)phenyl]silane | 194282-07-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Bis[4-(trifluoromethyl)phenyl]silane
• CAS: 194282-07-0
• 化学式: C₁₄H₁₀F₆Si
• 分子量: 320.309
• InChiKey: HNSHDLNANUKZMO-UHFFFAOYSA-N

物化性质

• 沸点：
  270.1±40.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.84
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  苯乙烯 、 Bis[4-(trifluoromethyl)phenyl]silane 在 [(IMes)Ni(styrene)₂] 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以63%的产率得到
  参考文献：
  名称：

  (NHC)Ni(0)-催化的支化选择性烯烃氢化硅烷化与仲和叔硅烷

  摘要：

  氢化硅烷化是构建有机硅烷的一种有价值的方法，有机硅烷是广泛应用于我们日常生活的有机硅材料的前体。该行业目前主要依赖于 Karstedt 的催化剂 Pt 2 (dvtms) 3 (dvtms = 1,3-二乙烯基四甲基二硅氧烷)，这是一种具有线性选择性的贵金属催化剂，而区域选择性有利于支化产物仍然是一个突出的挑战。使用更多地球丰富的贱金属催化剂一直是氢化硅烷化反应的最新焦点，大多数报告都集中在线性选择性催化剂的开发上，通常仅限于伯硅烷和/或仲硅烷。我们证明 (NHC)Ni(0) (NHC = N-杂环卡宾）配合物在烯烃与仲或叔硅烷（包括工业相关的烷氧基和氯硅烷）的支化选择性氢化硅烷化中具有活性。烯烃和硅烷的范围已经扩大到目前已知的镍催化氢化硅烷化反应，包括空间和电子分布。还进行了深入的机理研究，包括研究动力学和热力学反应参数的化学计量和催化实验。自由基陷阱实验表明反对单电子途径。反应的速率规律对

  DOI：

  10.1021/acscatal.2c03580

文献信息

• Thermal Isomerization of<i>mer</i>-[RhH(SAr)(SiHAr′₂)(PMe₃)₃] to<i>fac</i>-[RhH₂{SiAr′₂(SAr)}(PMe₃)₃] Involving Thiolato Group Transfer from Rh to Si
  作者：Kohtaro Osakada、Kouji Hataya、Takakazu Yamamoto

  DOI：10.1246/bcsj.71.2853

  日期：1998.12

  benzene or toluene solution of mer-[RhH(SAr)(SiHAr′2)(PMe3)3] (Ar = C6H5, C6H4Me-p, C6H4OMe-p; Ar′ = C6H5, C6H4Me-p, C6H4F-p, C6H4CF3-p) at 30—50 °C gives fac-[RhH2SiAr′2(SAr)}(PMe3)3] quantitatively through thiolato group transfer from Rh to Si. X-Ray structural analysis of fac-[RhH2SiPh2(SPh)}(PMe3)3] reveals octahedral coordination with three PMe3 ligands at facial coordination sites, while the 1H

  加热 mer-[RhH(SAr)(SiHAr'2)(PMe3)3] 的苯或甲苯溶液 (Ar = C6H5, C6H4Me-p, C6H4OMe-p; Ar' = , C6H4Me-p, C6H4F-p , C6H4CF3-p) 在 30-50 °C 下通过硫醇基从 Rh 转移到 Si 定量得到 fac-[RhH2SiAr'2(SAr)}(PMe3)3]。fac-[RhH2SiPh2(SPh)}(PMe3)3] 的 X 射线结构分析揭示了在面部配位位点与三个 PMe3 配体的八面体配位，而 1H NMR 光谱显示存在两个等效的氢化配体。其他Rh配合物通过核磁共振光谱法原位分离或表征。mer-[RhH(SC6H4Me-p)(SiHPh2)(PMe3)3]形成Rh配合物的反应服从一级动力学，动力学参数为：ΔG‡ = 98.6 kJ mol−1，ΔH‡ = 94.9 kJ mol −1，并且
• Structure and Chemical Properties of Chlorohydrido(diarylsilyl)rhodium(III) Complexes, <i>mer</i>-RhCl(H)(SiHAr₂)(PMe₃)₃. Thermally Induced Chloro Transfer from Rhodium to Silicon in the Complexes and Silane Exchange
  作者：Kohtaro Osakada、Susumu Sarai、Take-aki Koizumi、Takakazu Yamamoto

  DOI：10.1021/om970391z

  日期：1997.9.1

  Reactions of the diarylsilanes H2SiPh2, H2Si(C6H4Me-p)(2), H2Si(C6H4OMe-p)(2), H2Si(C6H4F-p)(2), and H2Si(C6H4CF3-P)(2) with [Rh(PMe3)(4)]Cl involve oxidative addition of an Si-H bond of the substrates to give mer-RhCl(H)[SiH(C6H4X-p)(2)](PMe3)(3) ( 1, X = H; 2, X = Me; 3, X = OMe; 4, X = F; 5, X = CF3). X-ray crystallography of 1, 3, 4, and 5 shows a distorted-octahedral coordination around the Rh center with three meridional PMe3 Ligands and with the chloro and diarylsilyl ligands at mutually trans positions. The Rh-Si bond distances of the complexes are in the range 2.311-2.319 Angstrom. Addition of H2Si(C6H4Me-p)(2) to a toluene solution of 1 results in partial conversion of the complex into 2 accompanied by liberation of H2SiPh2. The exchange of the diphenylsilyl ligand of 1 on addition of the other diarylsilanes proceeds reversibly at 10-50 degrees C with the thermodynamic parameters of the reactions 1 + H2Si(C6H4X-p)(2) = mer-RhCl(H)[SIH(C6H4X-p)(2)](PMe3)(3) + H2SiPh2 as Delta H degrees = 4.16 kJ mol(-1) and Delta S degrees = 8.2 J mol(-1) K-1 for X = Me, Delta H degrees = 6.51 kJ mol(-1) and Delta S degrees = 11.7 J mol(-1) K-1 for X = OMe, and Delta H degrees = -2.33 kJ mol(-1) and Delta S degrees = -5.3 J mol(-1) K-1 for X = F, respectively. Enthalpy of the reactions of 1 with H2Si(C6H4X-p)(2) (X = Me, OMe, and F) decreases with increase in the sigma(p) value of X. Heating a toluene solution of 1 at 50 degrees C and at 110 degrees C gives mixtures of fac-Rh(H)(2)(siClPh(2))(PMe3)(3) (6) and RhCl(H)(SiClPh2)(PMe3)(3) (7). The structure of 6 has been determined by X-ray crystallography, while 7 was characterized by comparison of the NMR (H-1, P-31H-1}, C-13H-1}, and Si-29H-1}) peaks with those of the complex prepared independently from the reaction of HSiClPh2 with [Rh(PMe3)(4)]Cl.