trimethylsilyl(di-p-tolylphosphanyl)acetylene

• 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: trimethylsilyl(di-p-tolylphosphanyl)acetylene
• 化学式: C₁₉H₂₃PSi
• 分子量: 310.451
• InChiKey: ZIKCEMJVJRJBHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.57
• 重原子数：
  21.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 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：

  trimethylsilyl(di-p-tolylphosphanyl)acetylene 在 甲醇 、 potassium carbonate 作用下， 以87%的产率得到di-p-tolylphosphanylethyne
  参考文献：
  名称：

  Reaction of Diphenylphosphanylacetylene with RB(C₆F₅)₂ Reagents: Evidence for a Remarkable Sequence of Synergistic Frustrated Lewis Pair Addition Reactions

  摘要：

  Diphenylphosphanylethyne (3a) reacts with tris(pentafluorophenyl)borane at room temperature by a typical frustrated Lewis pair (FLP) reaction. It undergoes a sequential series of 1,2-phosphane/borane additions to the alkyne unit in an overall 2:2 molar ratio to selectively form the dimeric product 5a. Product 5 features a pentafulvene-reminiscent structure with a pair of phosphonium units in the ring and B(C6F5)(3) substituents at the periphery. At elevated temperature, the reaction becomes less selective, now favoring the formation of cis- and trans-1,1-carboboration products from a 1:1 stoichiometry. After photolytic trans/cis isomerization, the vicinal FLP 6a becomes the major product, featuring an intramolecular P center dot center dot center dot B interaction. The reaction of 3a with H3CB(C6F5)(2) also gives a heterocyclic dimer (11), except that here a substituent H/CH3 exchange by an addition/elimination pathway has taken place. In the B(C6F5)(3)-derived system, we were able to trap an alleged intermediate of this rearrangement reaction by adding n-butyl isocyanide. Five products in the Ph2P- and (p-tolyl)(2)P-derived systems were characterized by X-ray diffraction

  DOI：

  10.1021/ic402139g
• 作为产物：
  描述：

  P,P-双(4-甲基苯基)-氯化膦 氯二对甲苯基膦 、 三甲基乙炔基硅 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以70%的产率得到trimethylsilyl(di-p-tolylphosphanyl)acetylene
  参考文献：
  名称：

  Reaction of Diphenylphosphanylacetylene with RB(C₆F₅)₂ Reagents: Evidence for a Remarkable Sequence of Synergistic Frustrated Lewis Pair Addition Reactions

  摘要：

  Diphenylphosphanylethyne (3a) reacts with tris(pentafluorophenyl)borane at room temperature by a typical frustrated Lewis pair (FLP) reaction. It undergoes a sequential series of 1,2-phosphane/borane additions to the alkyne unit in an overall 2:2 molar ratio to selectively form the dimeric product 5a. Product 5 features a pentafulvene-reminiscent structure with a pair of phosphonium units in the ring and B(C6F5)(3) substituents at the periphery. At elevated temperature, the reaction becomes less selective, now favoring the formation of cis- and trans-1,1-carboboration products from a 1:1 stoichiometry. After photolytic trans/cis isomerization, the vicinal FLP 6a becomes the major product, featuring an intramolecular P center dot center dot center dot B interaction. The reaction of 3a with H3CB(C6F5)(2) also gives a heterocyclic dimer (11), except that here a substituent H/CH3 exchange by an addition/elimination pathway has taken place. In the B(C6F5)(3)-derived system, we were able to trap an alleged intermediate of this rearrangement reaction by adding n-butyl isocyanide. Five products in the Ph2P- and (p-tolyl)(2)P-derived systems were characterized by X-ray diffraction

  DOI：

  10.1021/ic402139g

文献信息

• Formation of Unsaturated Vicinal Zr⁺/P Frustrated Lewis Pairs by the Unique 1,1-Carbozirconation Reactions
  作者：Xin Xu、Gerald Kehr、Constantin G. Daniliuc、Gerhard Erker

  DOI：10.1021/ja5068146

  日期：2014.9.3

  respectively. Complex 4a adds to the N═O functionality of nitrosobenzene with formation of 10. The vicinal M(+)/P systems 4 behave as reactive frustrated Lewis pairs toward hetercumulenes, undergoing 1,2-addition to the C═O bond of CO2 and the S═O bond of SO2 to form the respective adducts 11 and 12. The Zr(+)/P FLP 4a reacts with PhN═S═O to give the addition product 13, in which the phosphane Lewis base has

  用三甲基甲硅烷基（二芳基膦基）乙炔 Ar2P-C≡C-SiMe3（Ar = Ph 或 p）处理茂金属阳离子络合物 [Cp*2MCH3](+)[B(C6F5)4](-)（M = Zr 或 Hf） -tolyl) 导致在温和条件下通过独特的 1,1-碳金属化反应形成内部磷烷稳定的阳离子 [Cp*2M-C(CH3)=C(SiMe3)PAr2](+) 4。相比之下，当使用含有炔烃 (C6F5)2P-C≡C-SiMe3 的低路易斯碱度磷烷时，发生正常的 1,2-碳金属化生成配合物 5，显示出 Me-Si 基团与金属中心的配位. 配合物 4a 与正丁基异氰化物反应得到配位产物 6，其中保留了 Zr-P 键。用 N2O 处理 4a 通过磷烷的氧化得到五元金属杂环 7。邻位 M(+)/P 复合物 4 也显示出一些典型的 FLP 反应性。例如，它们添加到肉桂醛或多聚甲醛中，分别生成羰基加成产物 8 和 9。配合物
• Reaction of Diphenylphosphanylacetylene with RB(C₆F₅)₂ Reagents: Evidence for a Remarkable Sequence of Synergistic Frustrated <i>Lewis</i> Pair Addition Reactions
  作者：Jiangang Yu、Gerald Kehr、Constantin G. Daniliuc、Gerhard Erker

  DOI：10.1021/ic402139g

  日期：2013.10.7

  Diphenylphosphanylethyne (3a) reacts with tris(pentafluorophenyl)borane at room temperature by a typical frustrated Lewis pair (FLP) reaction. It undergoes a sequential series of 1,2-phosphane/borane additions to the alkyne unit in an overall 2:2 molar ratio to selectively form the dimeric product 5a. Product 5 features a pentafulvene-reminiscent structure with a pair of phosphonium units in the ring and B(C6F5)(3) substituents at the periphery. At elevated temperature, the reaction becomes less selective, now favoring the formation of cis- and trans-1,1-carboboration products from a 1:1 stoichiometry. After photolytic trans/cis isomerization, the vicinal FLP 6a becomes the major product, featuring an intramolecular P center dot center dot center dot B interaction. The reaction of 3a with H3CB(C6F5)(2) also gives a heterocyclic dimer (11), except that here a substituent H/CH3 exchange by an addition/elimination pathway has taken place. In the B(C6F5)(3)-derived system, we were able to trap an alleged intermediate of this rearrangement reaction by adding n-butyl isocyanide. Five products in the Ph2P- and (p-tolyl)(2)P-derived systems were characterized by X-ray diffraction