[1,1'-bis(diphenylphosphino)ethane(Pd(CH3)Cl)] | 64406-71-9

• 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: [1,1'-bis(diphenylphosphino)ethane(Pd(CH3)Cl)]
• 英文别名: (1,2-bis(diphenylphosphino)ethane)(CH3)PdCl；[PdCl(CH3)(bis(diphenylphosphino)ethane)]；Pd(methyl)Cl((C6H5)2PCH2CH2P(C6H5)2)；[Pd(dppe)(Me)(Cl)]；[PdCl(CH3)(1,2-bis(diphenylphosphino)ethane)]；[PdMe(Cl)(1,2-bis(diphenylphosphino)ethane)]
• CAS: 64406-71-9
• 化学式: C₂₇H₂₇ClP₂Pd
• 分子量: 555.332
• InChiKey: DSNAKLKQLFYCTM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.52
• 重原子数：
  31.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  [1,1'-bis(diphenylphosphino)ethane(Pd(CH3)Cl)] 在 HCl 作用下， 以 四氢呋喃 、 水 、 丙酮 、 乙腈 为溶剂， 生成 Pd(dppe)(OTf)₂
  参考文献：
  名称：

  阳离子钯（II）和铂（II）配合物中二甲硅烷基膦的环金属化：PH与​​CH活化

  摘要：

  阳离子络合物[M（dppe）（R）（PHMes 2）] [OTf]（M = Pd，R = Me（1），Ph（2）; M = Pt，R = Me（3），Et（4）;通过相应的M（dppe）（R）反应制得dppe = Ph 2 PCH 2 CH 2 PPh 2，Mes = 2,4,6-Me 3 C 6 H 2，OTf = OSO 2 CF 3）。 （X）（X = Cl，I），具有AgOTf和PHMes 2。当将它们放置在THF或CH 2 Cl 2溶液中时，Pd络合物进行环金属化反应，形成[Pd（dppe）（CH 2C 6 H 2（Me）2 PHMes）] [OTf]（5）。Pt配合物3和4的热解得到[Pt（dppe）（CH 2 C 6 H 2（Me）2 PHMes）] [OTf]（6），在后一种情况下还与乙烯一起。Pt（dppe）（Et）（Cl）与AgOTf的反应生成了[Pt（dppe）（H）]

  DOI：

  10.1021/om000164o
• 作为产物：
  描述：

  1,2-双(二苯基膦)乙烷 、 chloromethyl(1,5-cyclooctadiene)palladium(II) 以 苯 为溶剂， 以83%的产率得到[1,1'-bis(diphenylphosphino)ethane(Pd(CH3)Cl)]
  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

• A Comprehensive Mechanistic Picture of the Isomerizing Alkoxycarbonylation of Plant Oils
  作者：Philipp Roesle、Lucia Caporaso、Manuel Schnitte、Verena Goldbach、Luigi Cavallo、Stefan Mecking

  DOI：10.1021/ja508447d

  日期：2014.12.3

  olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced

  对异构化烷氧基羰基化的整个催化循环的理论研究表明，二膦配位的 Pd 中心周围的空间拥挤是选择性和生产率的决定性因素。异构化的能量分布对于可变空间体积的二膦是平坦的，但是对于空间要求高的二膦更倾向于形成直链 Pd-烷基物种。对于所有研究的 Pd-烷基物质，CO 插入是可行和可逆的，并且受二膦影响很小。与最高能量屏障相关的总体限速步骤是 Pd-酰基物质的甲醇分解。考虑到线性 Pd-酰基物质的甲醇分解，其能量势垒在所有研究的 Pd-酰基物质中最低，计算出的势垒对于更拥挤的二膦更低。计算表明，对于体积更大的二膦，线性与支化 Pd-酰基的甲醇分解能量差异更为明显，这是由于在过渡态中涉及不同数量的甲醇分子。在压力反应器条件下的实验研究表明，较短链烯烃底物的转化速度更快，但底物内的双键位置几乎没有影响。与高级烯烃相比，相同条件下的乙烯羰基化速度要快得多，这可能不仅是由于反应性线性酰基的出现，而且还因为烯
• 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。
• Insertion of sulfur dioxide into metalcarbon bonds of chloro(methyl)palladium complexes
  作者：Kelin Li、Ilia A Guzei、James Darkwa

  DOI：10.1016/s0277-5387(02)01377-3

  日期：2003.3

  Abstract Five chloro(methyl)palladium complexes (LL)Pd(Me)Cl have been shown to react with SO2 in solution to form S-sulfinato complexes of the formula (LL)Pd(SO2Me)Cl (LL=dippf=1,1′-bis(diisopropylphosphino)ferrocene (2), dppf=bis(diphenylphosphino)ferrocene (3), dppe=1,1′-bis(diphenylphosphino)ethane (4), COD (5) and (3,5-ditBupz)2 (6)). Compounds 5 and 6 are unstable in solution and slowly decompose

  摘要已有5种氯（甲基）钯配合物（LL）Pd（Me）Cl与溶液中的SO2反应形成S-磺胺基配合物，分子式为（LL）Pd（SO2Me）Cl（LL） = dippf = 1,1'-双（二异丙基膦基）二茂铁（2），dppf =双（二苯基膦基）二茂铁（3），dppe = 1,1'-双（二苯基膦基）乙烷（4），COD（5）和（ 3,5-ditBupz）2（6））。化合物5和6在溶液中不稳定并缓慢分解。报告了（dippf）Pd（Me）Cl（1）和（dppf）Pd（SO2Me）Cl（3）的代表性晶体结构。
• Synthesis and Structure of Dinuclear Diphosphine-Bridged Palladium(II) Complexes
  作者：Michael A. Zhuravel、David S. Glueck、Christopher D. Incarvito、Arnold L. Rheingold

  DOI：10.1021/om990378+

  日期：1999.10.1

  The dinuclear dicationic complexes [(Pd(dppe)(R))2(μ-diphos)]X2 (diphos = dppe; R = Ph (1), R = Me (2), diphos = dppp, R = Ph (3)) were prepared by the addition of a bidentate diphosphine to [Pd(dppe)(R)(PMes2H)]+, by treatment of [Pd(dppe)(R)(X)] (X = Cl, I) with Ag+ and a bidentate diphosphine, or by reaction of [Pd(dppe)(Ph)(X)] (X = Br, I) and dppe. NMR and crystal structure data show that the

  双核双金属配合物[[Pd（dppe）（R））2（μ-diphos）] X 2（diphos = dppe; R = Ph（1），R = Me（2），diphos = dppp，R = Ph（3））是通过在[Pd（dppe）（R）（PMes 2 H）] +中添加双齿二膦而制备的，方法是处理[Pd（dppe）（R）（X）]（X = Cl，I ）与Ag +和双齿二膦，或通过[Pd（dppe）（Ph）（X）]（X = Br，I）和dppe反应。NMR和晶体结构数据表明，溶液和固态1的结构相同，并且可以在同一金属中心比较螯合物和桥连dppe配体的结构和光谱。