[Pd(COMe)Cl(1,3-bis(diphenylphosphino)propane)] | 139168-09-5

• 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(COMe)Cl(1,3-bis(diphenylphosphino)propane)]
• CAS: 139168-09-5
• 化学式: C₂₉H₂₉ClOP₂Pd
• 分子量: 597.369
• InChiKey: VHCWGZVSSIZBAV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.41
• 重原子数：
  34.0
• 可旋转键数：
  5.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [Pd(COMe)Cl(1,3-bis(diphenylphosphino)propane)] 、 乙烯 以 乙醚 、 二氯甲烷 为溶剂， 生成 [(1,3-bis(diphenylphosphino)propane)Pd(CH2CH2COCH3)][B(3,5-(CF3)2C6H3)4]
  参考文献：
  名称：

  (1,3-双(二苯基膦)丙烷)Pd(II)中心迁移插入反应的动力学研究及其与乙烯和一氧化碳交替共聚的关系

  摘要：

  已经检查了与乙烯和 CO 通过高活性（dppp）Pd（II）基催化剂共聚相关的三个迁移插入过程的定量细节。在低温下生成并通过 1H、13C 和 31P NMR 光谱表征的阳离子 Pd(II) 中间体包括 (dppp)Pd(C2H4)(R)+ (R = -CH3, -CH2CH3)、6 和 7；(dppp)Pd(CO)(R)+ (R = -CH3, -CH2CH3)，8和11；和 (dppp)Pd(C2H4)(COCH3)+, 13. 对这些物种的迁移插入反应的动力学研究确定了以下活化参数：6(ΔG⧧ = 16.6(1) kcal/mol (-45.6 °C)， ΔH⧧= 15.2(7) kcal/mol, ΔS⧧ = −6.2(2.9) eu), 7(ΔG⧧ = 16.3(1) kcal/mol (-33.7 °C), ΔH⧧ = 15.9(8) kcal/ mol, ΔS⧧ = -1.6(3

  DOI：

  10.1021/ja994251n
• 作为产物：
  描述：

  [PdCl(CH3)(bis(diphenylphosphino)propane)] 在 一氧化碳 作用下， 以 二氯甲烷-D2 为溶剂， 生成 [Pd(COMe)Cl(1,3-bis(diphenylphosphino)propane)]
  参考文献：
  名称：

  Influence of ligands and anions on the rate of carbon monoxide insertion into palladium-methyl bonds in the complexes (P-P)Pd(CH3)Cl and [(P-P)Pd(CH3)(L)]+SO3CF3- (P-P = dppe, dppp, dppb, dppf; L = CH3CN, PPh3)

  摘要：

  The preparation of the neutral complexes (P-P)Pd(CH3)Cl (P-P = 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), 1,1'-bis-(diphenylphosphino)ferrocene (dppf)) and the ionic complexes [(P-P)Pd(CH3)(CH3CN)]+SO3CF3-(P-P = dppe, dppp, dppb, dppf) is described. The ionic dppb complex was formed as a mixture of monomeric and oligomeric forms, which can be attributed to the length and the flexibility of the backbone of the ligand. The rate of CO insertion into the Pd-CH3 bond in these complexes has been studied. The rate was found to decrease in the order dppb almost-equal-to dppp > dppf for the neutral complexes with half-life times ranging from 18 to 36 min at 235 K and 25 bar of CO. The dppe complex reacted much slower with a half-life time of 170 min at 305 K. The rate of carbonylation of the Pd-CH3 bond in the cationic complexes was at least 10 times higher than those of the analogous neutral complexes, the order being dppb almost-equal-to dppp almost-equal-to dppf > dppe with half-life times < 1.5 min at 235 K, except for the dppe complex, for which a half-life time of 2.5 min was measured. Carbonylation of the ionic PPh3-coordinated complex [(dppp)Pd(CH3)(PPh3)]+-SO3CF3- was at least 2.5 times slower than that of the analogous CH3CN-coordinated cationic complex.

  DOI：

  10.1021/om00040a034

文献信息

• Studies of Ligand and Solvent Effects in the Alternating Copolymerization of Carbon Monoxide and Ethene by Palladium-Diphosphine Catalysis
  作者：Claudio Bianchini、Andrea Meli、Gaby Müller、Werner Oberhauser、Elisa Passaglia

  DOI：10.1021/om020461o

  日期：2002.11.1

  activity and energy barriers to migratory insertions [Pd(Me)(CO), Pd(COMe)(C2H4)] as well as opening of β-chelates [Pd(CH2CH2C(O)Me)(P−P)]+ by CO. It is concluded that the presence and/or stereochemistry of methyl groups in the 1,3-positions of dppp do not exert a significant influence on the propagation rate of the copolymerization reaction in CH2Cl2. High-pressure NMR studies under catalytic conditions

  Pd（II）甲基络合物[Pd（Me）（MeCN）（P-P）] PF 6是一氧化碳与乙烯在CH 2 Cl 2中交替共聚的有效催化剂前体（PP = 1,3-双（二苯基膦基）丙烷（DPPP），内消旋-2,4-双（二苯基膦基）戊烷（内消旋-bdpp），外消旋-2,4-双（二苯基膦基）戊烷（外消旋-bdpp））。在30分钟内于高分子量聚酮的生产率如下配体顺序DPPP>内消旋-bdpp>外消旋-bdpp。所有甲基前体均表现出可比性的内在活性和迁移插入的能垒[Pd（Me）（CO），Pd（COMe）（C 2 H4）]和β-螯合物[Pd（CH 2 CH 2 C（O）Me）（P-P）] +通过CO的开放。结论是1中甲基的存在和/或立体化学DPPP的3-位对CH 2 Cl 2中共聚反应的传播速率没有显着影响。催化条件下的高压NMR研究表明，不规则水通过质子分解产生链转移，从而生成μ-羟基化合物[Pd（μ-OH）（P-P）]