triethyl(phenylmethoxy-d)silane | 1291054-56-2

• 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: triethyl(phenylmethoxy-d)silane
• CAS: 1291054-56-2
• 化学式: C₁₃H₂₂OSi
• 分子量: 223.395
• InChiKey: PVEFGVHUGAHUHQ-UQBWLURTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.21
• 重原子数：
  15.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  三乙基(硅烷-d) 、 苯甲醛 在 [(N,N-bis(2-C₆F₅-aminoethyl)methylamine)Re(CO)(OAc)] 作用下， 以 neat (no solvent) 为溶剂， 反应 24.0h， 生成 triethyl(phenylmethoxy-d)silane
  参考文献：
  名称：

  Role of Low-Valent Rhenium Species in Catalytic Hydrosilylation Reactions with Oxorhenium Catalysts

  摘要：

  The catalytic competency of a Re(III) complex has been demonstrated. In the presence of silane, oxorhenium(V) catalysts are deoxygenated to produce species that are significantly more active than the metal oxo precursors in hydrosilylation reactions. The results presented suggest that, in evaluating mechanisms for catalytic hydrosilylation reactions that involve high-valent metal oxo complexes, the activity of species that may be generated by deoxygenation of the metal with silane should also be systematically investigated as potential catalysts.

  DOI：

  10.1021/om300654q

文献信息

• Highly Efficient Large Bite Angle Diphosphine Substituted Molybdenum Catalyst for Hydrosilylation
  作者：Subrata Chakraborty、Olivier Blacque、Thomas Fox、Heinz Berke

  DOI：10.1021/cs4004276

  日期：2013.10.4

  Treatment of the complex Mo(NO)Cl-3(NCMe)(2) with the large bite angle diphosphine, 2,2'-bis(diphenylphosphino)diphenylether (DPEphos) afforded the dinuclear species [Mo(NO)(P boolean AND P)Cl-2](2)[mu Cl](2) (P boolean AND P = DPEphos = (Ph2PC6H4)(2)O (1) 1 could be reduced in the presence of Zn and MeCN to the cationic complex [Mo(NO)(P boolean AND P)(NCMe)(3)](+)[Zn2Cl6](1/2)(2-) (2). In a metathetical reaction the [Zn2Cl6](1/2)(2-) counteranion was replaced with NaBAr4F (BAr4F = [B3,5-(CF3)(2)C6H3}(4)]) to obtain the [BAr4F](-) salt [Mo(NO)(P boolean AND P)(NCMe)(3)](+)[Bar(4)(F)](-) (3). 3 was found to catalyze hydrosilylations of various para substituted benzaldehydes, cyclohexanecarboxaldehyde, 2-thiophenecarboxaldehyde, and 2-furfural at 120 degrees C. A screening of silanes revealed primary and secondary aromatic silanes to be most effective in the catalytic hydrosilylation with 3. Also ketones could be hydrosilylated at room temperature using 3 and PhMeSiH2. A maximum turnover frequency (TOF) of 3.2 x 10(4) h(-1) at 120 degrees C and a TOF of 4400 h(-1) was obtained at room temperature for the hydrosilylation of 4-methoxyacetophenone using PhMeSiH2 in the presence of 3. Kinetic studies revealed the reaction rate to be first order with respect to the catalyst and silane concentrations and zero order with respect to the substrate concentrations. A Hammett study for various para substituted acetophenones showed linear correlations with negative rho values of -1.14 at 120 degrees C and -3.18 at room temperature.