[Pd(1,1'-bis(diphenylphosphino)ferrocene)(Me)(NCMe)](OTf) | 139168-18-6

• 英文名称: [Pd(1,1'-bis(diphenylphosphino)ferrocene)(Me)(NCMe)](OTf)
• CAS: 139168-18-6
• 化学式: CF₃O₃S*C₃₇H₃₄FeNP₂Pd
• 分子量: 865.969
• InChiKey: GSIOZIZFIQYFHO-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：

  [Pd(1,1'-bis(diphenylphosphino)ferrocene)(Me)(NCMe)](OTf) 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：

  [bis(diphenylphosphino)ferrocene(Pd(CH3)Cl)] 、 silver trifluoromethanesulfonate 在 乙腈 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 以79%的产率得到[Pd(1,1'-bis(diphenylphosphino)ferrocene)(Me)(NCMe)](OTf)
  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

• Methoxycarbonylation of Ethene by Palladium(II) Complexes with 1,1‘-Bis(diphenylphosphino)ferrocene (dppf) and 1,1‘-Bis(diphenylphosphino)octamethylferrocene (dppomf)
  作者：Claudio Bianchini、Andrea Meli、Werner Oberhauser、Piet W. N. M. van Leeuwen,*、Martin A. Zuideveld、Zoraida Freixa、Paul C. J. Kamer、Anthony L. Spek、Oleg V. Gusev、Alexander M. Kal'sin

  DOI：10.1021/om021049b

  日期：2003.6.1

  square-planar bis(aquo) palladium(II) complexes [Pd(H2O)2(dppf)](OTs)2 and [Pd(H2O)2(dppomf)](OTs)2 are effective catalysts for the methoxycarbonylation of ethene, yet they exhibit quite different selectivity:  the dppf-modified catalyst produces several low molecular weight oxygenates, spanning from methyl propanoate to alternating oligomers of carbon monoxide and ethene, while the dppomf catalyst yields exclusively

  方平面双（aqua）钯（II）络合物[Pd（H 2 O）2（dppf）]（OTs）2和[Pd（H 2 O）2（dppomf）]（OTs）2是有效的催化剂乙烯的甲氧基羰基化，但它们表现出截然不同的选择性：dppf改性的催化剂会产生几种低分子量的含氧化合物，范围从丙酸甲酯到一氧化碳和乙烯的交替低聚物，而dppomf催化剂仅产生丙酸甲酯（dppf = 1， 1'-双（二苯基膦基）二茂铁; dppomf = 1,1'-双（二苯基膦基）八甲基二茂铁; OTs = p-甲苯磺酸盐）。为了合理化两个催化系统的不同选择性，在高压釜和高压NMR管中，在各种实验条件下进行了乙烯的甲氧基羰基化反应。另外，为了阐明在催化过程中通过NMR观察到的中间物种的结构，已经合成了许多模型化合物。在交替共聚或选择性生产丙酸甲酯中进行了引发，繁殖和链转移步骤的模型反应。根据所有这些研究，可以得出结论，dppf前体的行为类似于任何其他Pd