Pd(styrene)(PMe2Ph)2 | 137515-74-3

• 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: Pd(styrene)(PMe2Ph)2
• 英文别名: dimethyl(phenyl)phosphane;palladium;styrene
• CAS: 137515-74-3
• 化学式: C₂₄H₃₀P₂Pd
• 分子量: 486.87
• InChiKey: RTKCNJKXIMNZLU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Pd(styrene)(PMe2Ph)2 以 正己烷 、 氘代甲苯 为溶剂， 生成 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：

  苯乙烯 、 trans-[PdEt2(PMe2Ph)2] 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 Pd(styrene)(PMe2Ph)2
  参考文献：
  名称：

  基于头到尾连接的异氰酸酯二聚体的五元palladacycle的环状四聚体及其在异氰酸酯的环三聚反应中的反应性†

  摘要：

  的反应[钯（苯乙烯）（PR 3）2 ]，从生成的反式- [PDET 2（PR 3）2 ]和苯乙烯，与2当量 室温下将异氰酸苄酯在THF中制得的五元环的非常规环状Pd-四聚体由有机异氰酸酯二聚体和钯组成，[Pd（PR 3）{– C（O）N（R）C（O）N（ R） - }] 4（PR 3 = PME 3，1 ; PR 3 = PME 2 PH，2）。另外，环状三聚体，（RNCO）3，3（R ＝苄基）作为催化产物产生。用4当量处理环状四聚体（1）。（1,2-双（二乙基膦基）乙烷）（DEPE）或（1,2-双（二甲基膦基）乙烷）（DMPE）等螯合膦容易引起金属环顺式[Pd {N （R）C（O）N（R）C（O）}（P〜P）]（P〜P = DEPE，4 ; P〜P = DMPE，5）以定量产率计算。相反，Pd（0）-PR 3与2当量的反应。N- CO （Ar = Ph，p - tolyl ，p -ClC

  DOI：

  10.1039/c5dt00534e