trans-Pd(SiF2Ph)(SiMe3)(PMe2Ph)2 | 157261-54-6

• 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: trans-Pd(SiF2Ph)(SiMe3)(PMe2Ph)2
• 英文别名: trans-Pd(SiMe3)(SiF2Ph)(PMe2Ph)2
• CAS: 157261-54-6
• 化学式: C₂₅H₃₆F₂P₂PdSi₂
• 分子量: 599.096
• InChiKey: GHUFJLIKMRUWSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  32.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 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：

  trans-Pd(SiF2Ph)(SiMe3)(PMe2Ph)2 、 二苯基乙炔 以 氘代甲苯 为溶剂， 以93%的产率得到Pd(PMe2Ph)2(diphenylacetylene)
  参考文献：
  名称：

  乙炔和烯烃催化双甲硅烷基化反应的新反应体系

  摘要：

  Reaction of diphenylacetylene (1a) with Me3SiSiF2Ph (1 equiv) in toluene in the presence of a palladium catalyst (1 mol %) generated in situ by mixing [Pd(eta3-allyl)CI]2 and PMe2Ph (2.2 equiv/Pd) was completed in 1.4 h at room temperature to give the bis-silylation product (Z)-1-(difluorophenylsilyl)-1,2-diphenyl-2-(trimethylsilyl)ethene (2a) in 95% yield. In similar catalytic systems, a variety of acetylenes and olefins, including 3-hexyne, 1-phenyl-1-propyne, phenylacetylene, 1-octyne, norbornene, styrene, and 1-octene, were bis-silylated in 64-96% yields. The highly reactive nature of the present catalytic system was studied in stoichiometric systems. The presumed intermediates trans-Pd(SiMe3)(SiF2Ph)L2 (L = PMe3 (4a), PMe2Ph (4b)) were prepared by oxidative addition of Me3SiSiF2Ph toward Pd(styrene)L2 complexes (L = PMe3 (3a), PMe2Ph (3b)). Complex 4b reacted with diphenylacetylene (3 equiv) in toluene-ds at -20-degrees-C to give the bis-silylation product (Z)-2a in 82% yield together with Pd(PhC=Ph)(PMe2Ph)2 (93%). Treatment of 4a with dimethyl acetylenedicarboxylate (1 equiv) in toluene at -20-degrees-C instantly formed a palladium(0) complex coordinated with bis-silylated olefin, Pd{(X)-(MeO2C)(Me3Si)C=C(SiF2Ph)(CO2Me)}(PMe3)2 (6). The structure of 6 was determined by an X-ray diffraction study. Crystal data for 6 THF : C21H38O4P2F2-Si2Pd.C4H8O, a = 15.585(2) angstrom, b = 12.438(2) angstrom, c = 17.652(2), beta = 93.86(1)-degrees, V = 3413.9(8) angstrom3, monoclinic P2(1)/n, Z = 4.

  DOI：

  10.1021/om00020a042
• 作为产物：
  描述：

  trans-[PdEt2(PMe2Ph)2] 以 正己烷 、 氘代甲苯 为溶剂， 生成 trans-Pd(SiF2Ph)(SiMe3)(PMe2Ph)2
  参考文献：
  名称：

  乙炔和烯烃催化双甲硅烷基化反应的新反应体系

  摘要：

  Reaction of diphenylacetylene (1a) with Me3SiSiF2Ph (1 equiv) in toluene in the presence of a palladium catalyst (1 mol %) generated in situ by mixing [Pd(eta3-allyl)CI]2 and PMe2Ph (2.2 equiv/Pd) was completed in 1.4 h at room temperature to give the bis-silylation product (Z)-1-(difluorophenylsilyl)-1,2-diphenyl-2-(trimethylsilyl)ethene (2a) in 95% yield. In similar catalytic systems, a variety of acetylenes and olefins, including 3-hexyne, 1-phenyl-1-propyne, phenylacetylene, 1-octyne, norbornene, styrene, and 1-octene, were bis-silylated in 64-96% yields. The highly reactive nature of the present catalytic system was studied in stoichiometric systems. The presumed intermediates trans-Pd(SiMe3)(SiF2Ph)L2 (L = PMe3 (4a), PMe2Ph (4b)) were prepared by oxidative addition of Me3SiSiF2Ph toward Pd(styrene)L2 complexes (L = PMe3 (3a), PMe2Ph (3b)). Complex 4b reacted with diphenylacetylene (3 equiv) in toluene-ds at -20-degrees-C to give the bis-silylation product (Z)-2a in 82% yield together with Pd(PhC=Ph)(PMe2Ph)2 (93%). Treatment of 4a with dimethyl acetylenedicarboxylate (1 equiv) in toluene at -20-degrees-C instantly formed a palladium(0) complex coordinated with bis-silylated olefin, Pd{(X)-(MeO2C)(Me3Si)C=C(SiF2Ph)(CO2Me)}(PMe3)2 (6). The structure of 6 was determined by an X-ray diffraction study. Crystal data for 6 THF : C21H38O4P2F2-Si2Pd.C4H8O, a = 15.585(2) angstrom, b = 12.438(2) angstrom, c = 17.652(2), beta = 93.86(1)-degrees, V = 3413.9(8) angstrom3, monoclinic P2(1)/n, Z = 4.

  DOI：

  10.1021/om00020a042

文献信息

• Reactions of bis(silyl)palladium(II) complexes with allyl halides. Synthesis of mono(silyl)palladium(II) halides and X-ray structure of trans-PdCl(SiF2Ph)(PMe2Ph)2
  作者：Fumiyuki Ozawa、Mitsuru Sugawara、Koh Hasebe、Tamio Hayashi

  DOI：10.1016/s0020-1693(99)00298-4

  日期：1999.12

  Reactions of trans-Pd(SiF2Ph)2L2 (L=PMe3 (1a), PMe2Ph (1b), PMePh2 (1c)) with allyl bromide readily proceeded in CH2Cl2 at −20°C to form CH2CHCH2SiF2Ph and the corresponding bromo(silyl)palladium complexes, trans-PdBr(SiF2Ph)L2 (2a–2c) in high selectivities. Treatment of 1a–1c with dry HCl in CH2Cl2 at −20°C gave silyl chloride complexes, trans-PdCl(SiF2Ph)L2 (3a–3c), respectively. Complexes 2a–2c

  的反应反式-Pd（SIF 2 PH）2大号2（L = PME 3（1A），PME 2 Ph（上图1b），PMePh 2（1C））用烯丙基溴在CH容易进行2氯2在-20℃下形成CH 2 CHCH 2的SiF 2 PH和相应的溴（甲硅烷）合钯络合物，反式-PdBr（SIF 2博士）L- 2（2A - 2C中高选择性）。1a – 1c的治疗在-20°C的条件下，用无水HCl在CH 2 Cl 2中的溶液分别得到甲硅烷基氯配合物，反式-PdCl（SiF 2 Ph）L 2（3a – 3c）。分离出配合物2a - 2c和3a - 3c并通过NMR光谱和/或元素分析进行​​表征。还通过X射线衍射研究鉴定了一种配合物，反式-PdCl（SiF 2 Ph）（PMe 2 Ph）2（3b）。讨论了双甲硅烷基络合物与烯丙基化合物与乙硅烷催化甲硅烷基化的相关性。