(1,5-cyclooctadiene)Pt(C6H4-4-OMe)(C6H5) | 791838-95-4

• 英文名称: (1,5-cyclooctadiene)Pt(C6H4-4-OMe)(C6H5)
• 英文别名: (COD)Pt(C6H4-4-OMe)(C6H5)
• CAS: 791838-95-4
• 化学式: C₂₁H₂₄OPt
• 分子量: 487.501
• InChiKey: MXGLZYUHEPKTKF-PHFPKPIQSA-N

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：

  1,1'-双(二苯基膦)二茂铁 、 (1,5-cyclooctadiene)Pt(C6H4-4-OMe)(C6H5) 以 苯 为溶剂， 以90%的产率得到(1,1'-bis(diphenylphosphino)ferrocene)Pt(C6H4-4-OMe)(C6H5)
  参考文献：
  名称：

  Distinct Electronic Effects on Reductive Eliminations of Symmetrical and Unsymmetrical Bis-Aryl Platinum Complexes

  摘要：

  Symmetrical bis-aryl platinum complexes (DPPF)Pt(C6H4-4-R)(2) (R = NMe2, OMe, CH3, H, Cl, CF3) and electronically unsymmetrical bis-aryl platinum complexes (DPPF)Pt(C6H4-4-R) (C6H4-4-X) (R = CH3, X = NMe2, OMe, H, Cl, F, CF3; R = OMe, X = NMe2, H, Cl, F, CF3; R = CF3, X = H, Cl, NMe2; and R = NMe2, X = H, Cl) were prepared, and the rates of reductive elimination of these complexes in the presence of excess PPh3 are reported. The platinum complexes reductively eliminated biaryl compounds in quantitative yields with first-order rate constants that were independent of the concentration of PPh3. Plots of Log(k(obs)/k(obs(H))) vs Hammett substituent constants (sigma) of the para substituents R and X showed that the rates of reductive elimination reactions depended on two different electronic properties. The reductive elimination from symmetrical bis-aryl platinum complexes occurred faster from complexes with more electron-donating para substituents R. However, reductive elimination from a series of electronically unsymmetrical bis-aryl complexes was not faster from complexes with the more electron-donating substituents. Instead, reductive elimination was faster from complexes with a larger difference in the electronic properties of the substituents on the two platinum-bound aryl groups. The two electronic effects can complement or cancel each other. Thus, this combination of electronic effects gives rise to complex, but now more interpretable, free energy relationships for reductive elimination.

  DOI：

  10.1021/ja0480365
• 作为产物：
  描述：

  (COD)Pt(C6H4-4-OMe)Cl 、 苯基溴化镁 在 ammonium chloride 作用下， 以 乙醚 为溶剂， 以87%的产率得到(1,5-cyclooctadiene)Pt(C6H4-4-OMe)(C6H5)
  参考文献：
  名称：

  Distinct Electronic Effects on Reductive Eliminations of Symmetrical and Unsymmetrical Bis-Aryl Platinum Complexes

  摘要：

  Symmetrical bis-aryl platinum complexes (DPPF)Pt(C6H4-4-R)(2) (R = NMe2, OMe, CH3, H, Cl, CF3) and electronically unsymmetrical bis-aryl platinum complexes (DPPF)Pt(C6H4-4-R) (C6H4-4-X) (R = CH3, X = NMe2, OMe, H, Cl, F, CF3; R = OMe, X = NMe2, H, Cl, F, CF3; R = CF3, X = H, Cl, NMe2; and R = NMe2, X = H, Cl) were prepared, and the rates of reductive elimination of these complexes in the presence of excess PPh3 are reported. The platinum complexes reductively eliminated biaryl compounds in quantitative yields with first-order rate constants that were independent of the concentration of PPh3. Plots of Log(k(obs)/k(obs(H))) vs Hammett substituent constants (sigma) of the para substituents R and X showed that the rates of reductive elimination reactions depended on two different electronic properties. The reductive elimination from symmetrical bis-aryl platinum complexes occurred faster from complexes with more electron-donating para substituents R. However, reductive elimination from a series of electronically unsymmetrical bis-aryl complexes was not faster from complexes with the more electron-donating substituents. Instead, reductive elimination was faster from complexes with a larger difference in the electronic properties of the substituents on the two platinum-bound aryl groups. The two electronic effects can complement or cancel each other. Thus, this combination of electronic effects gives rise to complex, but now more interpretable, free energy relationships for reductive elimination.

  DOI：

  10.1021/ja0480365

文献信息

• Transmetalation of arylpalladium and platinum complexes. Mechanism and factors to control the reaction
  作者：Yuji Suzaki、Takeyoshi Yagyu、Kohtaro Osakada

  DOI：10.1016/j.jorganchem.2006.05.064

  日期：2007.1

  article reviews recent studies on intra- and intermolecular transfer of the aryl ligand bonded to Pd(II) and Pt(II). Cationic arylpalladium complexes with bpy and THF ligands undergo intermolecular aryl group transfer to produce biaryl via a diarylpalladium intermediate. This reaction is applied to cyclization of cationic dinuclear arylpalladium complexes, affording the crown ether derivative with biphenylene

  本文综述了有关键合到Pd（II）和PT（II）上的芳基配体的分子内和分子间转移的最新研究。具有bpy和THF配体的阳离子芳基钯配合物经历分子间芳基转移，从而通过二芳基钯中间体生成联芳基。该反应用于阳离子二核芳基钯配合物的环化，得到具有联亚苯基单元的冠醚衍生物。类似的芳基铂配合物不会通过金属转移形成二芳基配合物，而与CO和苯丙二烯反应，分别引起配位溶剂的置换和小分子插入PT-C键中。PTCl 2（鳕鱼）和PTPh 2的配比（cod）产生PTCl（Ph）（cod），这是通过从前一个络合物中解离Cl配体而诱导的。PTCl 2（鳕鱼）也与带有bpy和dppe的二芳基铂配合物反应。PTPh（CH 2 COMe）（cod）歧化和PTPh 2（cod）和PT（CH 2 COMe）2（cod）歧化发生在50°C，但表观可逆反应的速率互不相同。OH的加成-到PTI（PH）（COD）的溶液导致的分子间配体的苯