[(trans-PhCH=CHPPh3)Pd(PPh3)Br]

• 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-PhCH=CHPPh3)Pd(PPh3)Br]
• 英文别名: [Pd((E)-η2-PhCH=CHPPh3)Br(PPh3)]；palladium;triphenyl-[(E)-2-phenylethenyl]phosphanium;triphenylphosphane;bromide
• 化学式: C₄₄H₃₇BrP₂Pd
• 分子量: 814.049
• InChiKey: AEBHJDZNRBKVFI-ZRUFZDNISA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  48
• 可旋转键数：
  8
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  trans-(E)-styrylbromobis(triphenylphosphine)palladium 以 二氯甲烷-D2 为溶剂， 生成 [(trans-PhCH=CHPPh3)Pd(PPh3)Br]
  参考文献：
  名称：

  从反式-[Pd（CH═CHPh）Br（PMePh 2）2 ]还原CP的机理

  摘要：

  的（ë） -和（Ž）的苯乙烯基异构体的反式- [钯（CH═CHPh）溴（PMePh 2）2 ]（1A）和[加入Pd（η 2 -PhCH═CHPMePh 2）能Br（PMePh 2）]制备（2a），并检查它们的CP还原消除（1a → 2a）和CP氧化添加（2a → 1a）行为。反应的动力学和热力学受到苯乙烯基的E / Z构型和溶剂极性的强烈影响。复合物（E）-1a容易在CD 2 Cl 2中作为极性溶剂以高选择性进行C-P还原消除。在另一方面，当（Ž） -异构体1A是朝向还原消除，（未反应的Ž） -图2a有利经历C肽氧化加成在非极性苯。X射线衍射分析和1a和2a的DFT计算为这些反应特征提供了合理的解释。动力学检查揭示了两种类型的C-P还原消除过程，分别涉及PMePh 2配体的预离解和缔合。

  DOI：

  10.1021/om801207k

文献信息

• Synthesis and Structure of η²-Phosphonioalkene−Palladium(0) Complexes. A Catalyst Intermediate in the Palladium-Mediated Synthesis of Alkenylphosphonium Halides
  作者：Chien-Chih Huang、Jiun-Pey Duan、Ming-Yuan Wu、Fen-Ling Liao、Sue-Lein Wang、Chien-Hong Cheng

  DOI：10.1021/om970709n

  日期：1998.2.1

  Treatment of Pd(PPh3)(4) with PhCH=CHBr in THF at 45 degrees C gave [(trans-PhCH=CHPPh3)Pd(PPh3)(2)]Br-+(-) (1), which was found to be converted from Pd(PPh3)(2)(CH=CHPh)Br. X-ray structural analysis shows that 1 adopts a distorted-square-planar geometry with two PPh3 ligands and a (PhCH=CHPPh3)(+) moiety. The C-C double bond in the latter is pi-bonded to the palladium(0) center and occupies two of the four square-planar coordination sites. Under similar reaction conditions, Pd[P-trans-PhCH=CHP(p-tolyl)(3)][P(p-tolyl)(3)](2)}Br-+(-) (2) was formed from Pd[P(p-tolyl)(3)](4) and PhCH=CHBr, while [(trans-MeCH=CHPPh3)Pd(PPh3)(2)]Br-+(-) (3) was isolated from the reactions of Pd(PPh3)4 with MeCH=CHBr. Treating PhCH=CHBr with trans-Pd(PPh3)(2)(C6H4O-p-CH3)I in THF at ambient temperature led to the formation of (trans-PhCH=CHPPh3)Pd(PPh3)X (5) and (p-CH3OC6H4PPh3)X-+(-) (X, mixture of Br and I). Complex 5 (X Br) can be prepared by treating trans-PhCH=CH(PPh3)Br-+(-) with Pd(dba)(2) and 1 equiv of PPh3 in CH2Cl2. X-ray analysis shows 5 adopts a distorted-square-planar structure consisting of PPh3, X, and PhCH=CH(PPh3)(+) as ligands. The PPh3 ligand is trans to the olefin carbon that is connected to the PPh3 group in PhCH=CH(PPh3)(+), while the halide ligand is trans to the olefin carbon bonded to a phenyl moiety. Reaction of 5 (X = Br) with 1 equiv of PPh3 at ambient temperature afforded 1 in high yield. Pd(PPh3)(4) or Pd(OAc)(2) catalyzes the reactions of PPh3 with PhCH=CHBr, MeCH=CHBr, MeCH=C(Me)Br (mixtures of isomers), CH2=C(Me)Br, cis-(EtO2C)CH=CHBr, and cis-(MeO2C)CH=CHBr to give the corresponding trans-RCH=CR'(PPh3)Br-+(-). During the reaction of PPh3 with PhCH-CHBr, 1 was found to be a catalyst intermediate in the reaction solution. All the pho sphonioalkene-palladium(0) complexes and alkenylphosphonium halides isolated are trans in the (RCH-CR'PPh3)(+) moiety.
• Mechanism of C−P Reductive Elimination from <i>trans</i>-[Pd(CH═CHPh)Br(PMePh₂)₂]
  作者：Masayuki Wakioka、Yumiko Nakajima、Fumiyuki Ozawa

  DOI：10.1021/om801207k

  日期：2009.4.27

  trans-[Pd(CH═CHPh)Br(PMePh2)2] (1a) and [Pd(η2-PhCH═CHPMePh2)Br(PMePh2)] (2a) were prepared, and their C−P reductive elimination (1a → 2a) and C−P oxidative addition (2a → 1a) behaviors examined. Kinetics and thermodynamics of the reactions are strongly affected by E/Z configurations of the styryl group and solvent polarity. Complex (E)-1a readily undergoes C−P reductive elimination in CD2Cl2 as a polar solvent

  的（ë） -和（Ž）的苯乙烯基异构体的反式- [钯（CH═CHPh）溴（PMePh 2）2 ]（1A）和[加入Pd（η 2 -PhCH═CHPMePh 2）能Br（PMePh 2）]制备（2a），并检查它们的CP还原消除（1a → 2a）和CP氧化添加（2a → 1a）行为。反应的动力学和热力学受到苯乙烯基的E / Z构型和溶剂极性的强烈影响。复合物（E）-1a容易在CD 2 Cl 2中作为极性溶剂以高选择性进行C-P还原消除。在另一方面，当（Ž） -异构体1A是朝向还原消除，（未反应的Ž） -图2a有利经历C肽氧化加成在非极性苯。X射线衍射分析和1a和2a的DFT计算为这些反应特征提供了合理的解释。动力学检查揭示了两种类型的C-P还原消除过程，分别涉及PMePh 2配体的预离解和缔合。