Pd(styrene)(PMePh2)2 | 70316-76-6

• 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: Pd(styrene)(PMePh2)2
• 英文别名: [(styrene)bis(methyldiphenylphosphine)palladium(0)]；[Pd(styrene)(P(CH3)(C6H5)2)2]；methyl(diphenyl)phosphane;palladium;styrene
• CAS: 70316-76-6
• 化学式: C₃₄H₃₄P₂Pd
• 分子量: 611.011
• InChiKey: BDMGUNJQCISSMO-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)(PMePh2)2 、 1,1,2,2-Tetrafluordiphenyldisilan 以 甲苯 为溶剂， 以78%的产率得到trans-Pd(SiF2Ph)2(PMePh2)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
• 作为产物：
  描述：

  trans-PdEt2(PMePh2)2 、 苯乙烯 以 氘代甲苯 为溶剂， 生成 Pd(styrene)(PMePh2)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

• Synthesis of Unsymmetrical Ketones by Palladium-Catalyzed Cross-Coupling Reaction of Carboxylic Anhydrides with Organoboron Compounds
  作者：Ryuki Kakino、Sayaka Yasumi、Isao Shimizu、Akio Yamamoto

  DOI：10.1246/bcsj.75.137

  日期：2002.1

  anhydrides to zerovalent palladium complexes to yield acyl(carboxylato)bis(tertiary phosphine)palladium(II) complexes and their reactions with organoboronic acids to yield ketones, a novel catalytic process has been developed. This converts carboxylic anhydrides and organoboron compounds into ketones catalyzed by palladium complexes under mild conditions. The process provides a general, versatile, synthetic

  在对羧酸酐与零价钯配合物氧化加成生成酰基（羧基）双（叔膦）钯 (II) 配合物及其与有机硼酸反应生成酮的基础研究的基础上，开发了一种新的催化工艺。这在温和条件下将羧酸酐和有机硼化合物转化为由钯配合物催化的酮。该方法提供了一种通用的、通用的合成方法来生产具有芳香族、脂肪族和杂环基团的各种对称和不对称酮。建议催化循环包括（a）羧酸酐的氧化加成以产生酰基（羧基）钯中间体，（b）与有机硼化合物进行金属转移以产生酰基（有机）钯中间体，(c) 还原消除生成酮。发现不仅均相催化剂体系而且非均相体系在温和条件下产生酮。
• Dipalladium complexes with bridging diorganosilyl ligands. Synthesis, structure, and properties of [LPd(μ-SiH(R)Ph)]2 (R = Ph or Me; L = PMe3, PEt3 or PMePh2)
  作者：Yong-Joo Kim、Sang-Chul Lee、Jong-Il Park、Kohtaro Osakada、Jun-Chul Choi、Takakazu Yamamoto

  DOI：10.1039/a907745f

  日期：——

  trans-PdEt2L2 (L = PMe3, PEt3 or PMePh2) reacted with equimolar or twofold molar amounts of H2SiPh2 to produce various bimetallic palladium(II) complexes with bridging diphenylsilyl ligands, [(Me3P)Pd(μ-SiHPh2)]21, (Me3P)Pd(μ-SiHPh2)Pd(PMe3)22 and [LPd(μ-SiHPh2)]2 (L = PEt33 or PMePh24), in moderate to good yields. Similar reactions using H2SiMePh afforded the complexes [LPd(μ-SiHMePh)]2 (L = PMe35 or PEt36)

  复合物的反式-PdEt 2大号2（L = PME 3，PET 3或PMePh 2）用等摩尔或两倍摩尔量的H的反应2 SIPH 2以产生各种双金属钯（II）与二苯基桥接的复合物配体，[（ME 3 P）的Pd（μ-SiHPh 2）] 2 1，（ME 3 P）的Pd（μ-SiHPh 2）的Pd（PME 3）2 2和[LPD（μ-SiHPh 2）] 2（L = PEt 3 3或PMePh 2 4），产率中等至良好。使用H 2 SiMePh进行的类似反应得到络合物[LPd（μ-SiHMePh）] 2（L = PMe 3 5或PEt 3 6）。分离的复合物的特征在于核磁共振波谱和元素分析。3和5的分子结构已通过X射线晶体学并建议μ-SiHPh之间的抓氢键2或μ-SiHMePh组和钯。这核磁共振 对配合物的研究揭示了桥联的协调作用。 甲硅烷基 配体具有类似于固态的溶液中的Si–H–Pd三中心，两电子键。复合物2经历了PMe
• SON, TAE-IL;YANAGIHARA, HISAYOSHI;OZAWA, FUMIYUKI;YAMAMOTO, AKIO, BULL. CHEM. SOC. JAP., 61,(1988) N 4, 1251-1258
  作者：SON, TAE-IL、YANAGIHARA, HISAYOSHI、OZAWA, FUMIYUKI、YAMAMOTO, AKIO

  DOI：——

  日期：——