| 139168-14-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• CAS: 139168-14-2
• 化学式: CF₃O₃S*C₃₀H₃₂NP₂Pd
• 分子量: 724.029
• InChiKey: RMWRRTDHXHLJHG-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：

  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：

  [PdCl(CH3)(bis(diphenylphosphino)propane)] 、 silver trifluoromethanesulfonate 在 乙腈 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 以84%的产率得到
  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

• Synthesis, characterization and reactivity of ionic palladium(II) complexes containing bidentate nitrogen ligands in a unidentate coordination mode,
  作者：J.H. Groen、B.J. de Jong、J.-M. Ernsting、P.W.N.M. van Leeuwen、K. Vrieze、W.J.J. Smeets、A.L. Spek

  DOI：10.1016/s0022-328x(98)00596-8

  日期：1999.1

  phen, dppe and dppp ligands, as compared with that of the p-An-BIAN ligand. In contrast, complex 3a (LL=dmphen) contains a bidentate p-An-BIAN ligand and a unidentate dmphen ligand, which can be explained by the sterically demanding methyl groups of the dmphen ligand. Complexes 1a–4a underwent insertion of carbon monoxide, resulting in the formation of acetylpalladium complexes [Pd(C(O)Me)(p-An-BIAN)(LL)]SO3CF3

  新型离子络合物[Pd（Me）（p -An-BIAN）（LL）] SO 3 CF 3（LL= p -An-BIAN（bis（anisylimino）acenaphthene）（1a），phen（2a），dmphen（3a），dppe（4a），dppp（5a））是通过[Pd（Me）（NCMe）（p -An- BIAN ）] SO 3 CF 3与LL反应合成的。配合物1a的X射线晶体结构已确定并显示了扭曲的正方形平面几何形状，其中一个BIAN配体以双齿形式配位（PdN（1）= 2.037（4）Å;PdN（2）= 2.189（4）Å），并且有趣的是，另一个BIAN配体以不相同的方式出现（PdN（3）= 2.066（4）Å；PdN（4）= 2.714（6）Å）。混合的配体配合物[Pd（Me）（p -An-BIAN）（LL）] SO 3 CF 3（LL= phen（2a），dppe（
• Chain-Transfer Mechanisms of the Alternating Copolymerization of Carbon Monoxide and Ethene Catalyzed by Palladium(II) Complexes:  Rearrangement to Highly Reactive Enolates
  作者：Martin A. Zuideveld、Paul C. J. Kamer、Piet W. N. M. van Leeuwen、Peter A. A. Klusener、Hans A. Stil、Cornelis F. Roobeek

  DOI：10.1021/ja980914+

  日期：1998.8.1
• In Situ Monitoring of a Heterogeneous Palladium-Based Polyketone Catalyst
  作者：Wilhelmus P. Mul、Heiko Oosterbeek、Gerhard A. Beitel、Gert-Jan Kramer、Eite Drent

  DOI：10.1002/(sici)1521-3773(20000515)39:10<1848::aid-anie1848>3.0.co;2-8

  日期：2000.5.15