[bis(diphenylphosphino)ferrocene(Pd(CH3)Cl)] | 139198-75-7

• 英文名称: [bis(diphenylphosphino)ferrocene(Pd(CH3)Cl)]
• 英文别名: [Pd(dppf)MeCl]；[1,1'-bis(diphenylphosphino)ferrocene]Pd(CH3)Cl；[Pd(Me)Cl(dppf)]；(dppf)Pr(Me)Cl
• CAS: 139198-75-7
• 化学式: C₃₅H₃₁ClFeP₂Pd
• 分子量: 711.299
• InChiKey: ZHUOPIGSFREPDI-UHFFFAOYSA-M

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：

  [bis(diphenylphosphino)ferrocene(Pd(CH3)Cl)] 在 一氧化碳 作用下， 以 二氯甲烷-D2 为溶剂， 生成
  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：

  1,1'-双(二苯基膦)二茂铁 、 chloromethyl(1,5-cyclooctadiene)palladium(II) 以 苯 为溶剂， 以85%的产率得到[bis(diphenylphosphino)ferrocene(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

• Mechanistic Studies of the Palladium-Catalyzed Ring Opening of Oxabicyclic Alkenes with Dialkylzinc
  作者：Mark Lautens、Sheldon Hiebert、Jean-Luc Renaud

  DOI：10.1021/ja010498k

  日期：2001.7.1

  The mechanism of the palladium-catalyzed ring opening of oxabicyclic alkenes with dialkylzinc has been studied. Experiments which rule out a π-allyl mechanism were carried out. Trapping carbometalated products and synthesis and successful reaction of alkyl palladium species provided strong evidence in favor of an enantioselective carbopalladation as the key step in the mechanism. The studies also suggest

  研究了钯催化氧化二环烯烃与二烷基锌的开环机理。进行了排除π-烯丙基机制的实验。捕获碳金属化产物以及烷基钯物种的合成和成功反应为支持对映选择性碳钯化作为该机制的关键步骤提供了强有力的证据。研究还表明，阳离子钯物种负责烯烃的碳钯化。钯和二烷基锌的组合是独特的，因为二烷基锌在金属转移中起到钯的作用，并且在形成反应性阳离子钯物质时作为路易斯酸起作用。
• Application of Methyl Bisphosphine-Ligated Palladium Complexes for Low Pressure <i>N</i> -¹¹ C-Acetylation of Peptides
  作者：Thomas L. Andersen、Patrik Nordeman、Heidi F. Christoffersen、Hélène Audrain、Gunnar Antoni、Troels Skrydstrup

  DOI：10.1002/anie.201700446

  日期：2017.4.10

  described for 11C‐labeling of peptides selectively at the N‐terminal nitrogen or at internal lysine positions. The presented method relies on the use of specific biphosphine palladium–methyl complexes and their high reactivity towards amino‐carbonylation of amine groups in the presence [11C]carbon monoxide. The protocol facilitates the production of native N‐11C‐acetylated peptides, without any structural

  描述了一种温和有效的方法，可选择性地在N端氮或赖氨酸内部位置对肽进行11 C标记。提出的方法依赖于特定的双膦钯-甲基络合物的使用及其在[ 11 C]一氧化碳存在下对氨基的氨基羰基化的高反应性。该方案可促进天然N - 11 C-乙酰化肽的生产，而无需进行任何结构修饰，并且已应用于选择生物活性肽。
• 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。
• Studies on AlkylNitrogen Bond Formation<i>via</i>Reductive Elimination from Monomeric Palladium Complexes in High Oxidation State
  作者：Álvaro Iglesias、Kilian Muñiz

  DOI：10.1002/hlca.201200430

  日期：2012.10

  palladium(II) complexes bearing a bidentate ligand, and a methyl and an amidato substituent was carried out with the aim to gain a better understanding of the inherent requirements for CN bond‐formation from Pd complexes in high oxidation state. This work clarified the role of the individual nitrogen sources and has important implication for alkylnitrogen bond‐forming reactions catalyzed by Pd.

  的一系列定义的钯（II）配合物带有二齿配体，和一个甲基和一个amidato取代基是用目的进行氧化，以便更好地的对C内在要求理解 N键-形成选自Pd络合物在高氧化态。这项工作阐明了各个氮源的作用，并且对Pd催化的烷基氮键形成反应具有重要意义。
• 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。