[PdCl(CH3)(bis(diphenylphosphino)propane)] | 139168-06-2

• 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: [PdCl(CH3)(bis(diphenylphosphino)propane)]
• 英文别名: Pd(dppp)MeCl；[Pd(Me)Cl(1,3-bis(diphenylphosphino)propane)]；[PdCl(Me)(1,3-bis(diphenylphosphino)propane)]；chloride(methyl)palladium(II)(dppp)；[Pd(Me)Cl(dppp)]；[PdCl(Me)(dppp)]
• CAS: 139168-06-2
• 化学式: C₂₈H₂₉ClP₂Pd
• 分子量: 569.359
• InChiKey: VUAWEJSMGLKRIC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.91
• 重原子数：
  32.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  [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
• 作为产物：
  描述：

  1,3-双(二苯基膦)丙烷 、 chloromethyl(1,5-cyclooctadiene)palladium(II) 以 苯 为溶剂， 以94%的产率得到[PdCl(CH3)(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
• 作为试剂：
  描述：

  methyl (4-isocyano-3-(propa-1,2-dien-1-yl)benzoyl)-L-leucinate 在 [PdCl(CH3)(bis(diphenylphosphino)propane)] 、 sodium tetrahydroborate 作用下， 以 二氯甲烷 、 四氢呋喃 为溶剂， 反应 1.17h， 以5 mg的产率得到
  参考文献：
  名称：

  使用氨基酸侧链的取代基增强 π 堆叠螺旋结构的稳定性：通过成核-伸长机制形成螺旋

  摘要：

  涉及将α-氨基酸残基掺入聚合物的侧链或主链的分子设计通常用于通过分子内氢键来稳定人工分子结构。然而，这种分子设计策略很少考虑氨基酸部分 α 位取代基之间相互作用的重要性，如自然界中发现的那样。在此，我们报告了一系列新型 π 堆叠螺旋聚 (quinolylene-2,3-methylene) 的合成，其中氨基酸衍生物在 α 位具有不同的取代基。我们发现通过将取代基填充在侧链之间的空白空间中，π-堆叠螺旋聚（喹啉-2,3-亚甲基）的热稳定性得到显着提高。特别是，当使用庞大的环己基丙氨酸衍生物作为侧链时，即使在氢键竞争者二甲亚砜中，π-堆叠螺旋结构也能保持其稳定性。氨基酸取代基对 π 堆叠结构的稳定作用导致了独特的聚合行为，涉及成核-伸长步骤。在具有亮氨酸和环己基丙氨酸的衍生物形成稳定的π-堆叠螺旋结构的情况下，在初始聚合阶段形成具有缠结主链的亚稳态结构。这些结构随后经历了不可逆的结构变化，以实现热力学稳定的螺旋

  DOI：

  10.1021/jacs.2c01337

文献信息

• Carbon−Sulfur Bond-Forming Reductive Elimination Involving sp-, sp²-, and sp³-Hybridized Carbon. Mechanism, Steric Effects, and Electronic Effects on Sulfide Formation
  作者：Grace Mann、David Baranano、John F. Hartwig、Arnold L. Rheingold、Ilia A. Guzei

  DOI：10.1021/ja981428p

  日期：1998.9.1

  alkynyl sulfides. Reductive eliminations forming alkenyl alkyl sulfides and aryl alkyl sulfides were the fastest. Eliminations of alkynyl alkyl sulfides were slower, and elimination of dialkyl sulfide was the slowest. Thus the relative rates for sulfide elimination as a function of the hybridization of the palladium-bound carbon follow the trend sp2 > sp ≫ sp3. Rates of reductive elimination were faster

  钯硫合络合物 [(L)Pd(R)(SR')]，其中 L 是螯合配体，例如 DPPE、DPPP、DPPBz、DPPF 或 TRANSPHOS，R 是甲基、烯基、芳基或炔基配体， R'是芳基或烷基，通过取代或质子转移反应合成。发现所有这些硫醇盐配合物都以高产率进行碳硫键形成还原消除，以形成二烷基硫化物、二芳基硫化物、烷基芳基硫化物、烷基烯基硫化物和烷基炔基硫化物。形成烯基烷基硫化物和芳基烷基硫化物的还原消除是最快的。炔基烷基硫化物的消除较慢，二烷基硫化物的消除最慢。因此，作为钯结合碳杂化函数的硫化物消除的相对速率遵循趋势 SP2 > SP ≫ SP3。对于具有较大咬合角的顺式螯合膦配体，还原消除速率更快。动力学研究，以及自由基捕获的结果……
• Insertion of Imines into Palladium-Acyl Bonds: Towards Metal-Catalyzed Alternating Copolymerization of Imines with Carbon Monoxide To Form Polypeptides
  作者：Smita Kacker、Jang Sub Kim、Ayusman Sen

  DOI：10.1002/(sici)1521-3773(19980518)37:9<1251::aid-anie1251>3.0.co;2-4

  日期：1998.5.18

  From a methyl ligand, CO, and an imine a chelating amide ligand is formed by insertion of the C=N bond into the metal-acyl bond in cationic palladium(II) complexes (see reaction below). The cationic acylpalladium complexes are obtained from CO and readily accessible palladium starting materials. LL=diphosphane ligand.

  由甲基配体，CO和亚胺，通过将C = N键插入阳离子钯（II）配合物中的金属-酰基键中，形成螯合酰胺配体（请参见以下反应）。阳离子酰基铝配合物是从一氧化碳和易于获得的钯原料中获得的。LL ＝二膦配体。
• Kinetic Studies of Migratory Insertion Reactions at the (1,3-Bis(diphenylphosphino)propane)Pd(II) Center and Their Relationship to the Alternating Copolymerization of Ethylene and Carbon Monoxide
  作者：C. Scott Shultz、John Ledford、Joseph M. DeSimone、Maurice Brookhart

  DOI：10.1021/ja994251n

  日期：2000.7.1

  of three migratory insertion processes relevant to the copolymerization of ethylene and CO by the highly active (dppp)Pd(II)-based catalyst have been examined. Cationic Pd(II) intermediates generated at low temperatures and characterized by 1H, 13C and 31P NMR spectroscopy include (dppp)Pd(C2H4)(R)+ (R = −CH3, −CH2CH3), 6 and 7; (dppp)Pd(CO)(R)+ (R = −CH3, −CH2CH3), 8 and 11; and (dppp)Pd(C2H4)(COCH3)+

  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, -CH2 )、6 和 7；(dppp)Pd(CO)(R)+ (R = - , -CH2 )，8和11；和 (dppp)Pd( )(CO )+, 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
• 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）]
• Palladium Chemistry with Stanna‐ <i>closo</i> ‐dodecaborate and Isocyanides
  作者：Martin Hornung、Lars Wesemann

  DOI：10.1002/ejic.201000292

  日期：2010.7

  equilibrium between isocyanides and stanna-closo-dodecaborate with palladium(II) was investigated. The mixed substituted products of type [(RNC) 2 Pd-(SnB 11 H 11 ) 2 ] 2 and [(RNC)Pd(SnB 11 H 11 ) 3 ] 4- were characterized by X-ray crystal structure analysis, elemental analysis and NMR spectroscopy. Isocyanide insertion into palladium-carbon bonds was also found. The zwitterionic complexes isolated from

  研究了异氰化物和锡-氯-十二硼酸盐与钯 (II) 之间的取代平衡。[(RNC) 2 Pd-(SnB 11 H 11 ) 2 ] 2 和[(RNC)Pd(SnB 11 H 11 ) 3 ] 4-型混合取代产物通过X射线晶体结构分析、元素分析表征和核磁共振光谱。还发现了异氰化物插入钯-碳键。从[(P' 2 )Pd(Me)(SnB 11 H 11 )]-(P' 2 = dppe, dppp, dppf) 与异氰化物的反应中分离出的两性离子复合物进行了表征。