[(1,3-bis(diphenylphosphino)propane)Pd(COMe)(CO)][B(C6F5)4] | 524936-94-5

• 英文名称: [(1,3-bis(diphenylphosphino)propane)Pd(COMe)(CO)][B(C6F5)4]
• 英文别名: [(dppp)Pd(COMe)(CO)][B(C6F5)4]
• CAS: 524936-94-5
• 化学式: C₂₄BF₂₀*C₃₀H₂₉O₂P₂Pd
• 分子量: 1268.97
• InChiKey: QIPFBBYNXWYVPK-UHFFFAOYSA-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：

  氯乙烯 、 [(1,3-bis(diphenylphosphino)propane)Pd(COMe)(CO)][B(C6F5)4] 在 LiCl 、 Et₂O 作用下， 以 乙醚 为溶剂， 生成 [(1,3-bis(diphenylphosphino)propane)Pd(CHClCH2COMe)][B(C6F5)4]
  参考文献：
  名称：

  Reaction of Vinyl Chloride with Cationic Palladium Acyl Complexes

  摘要：

  Vinyl chloride (VC) reacts with the cationic Pd complexes [L2Pd(Me)(CO)] [B(C6F5)(4)] (3a-d; L-2 = Me(2)bipy, (t)Bu(2)bipy, dppp, dmpe) and [L2Pd{C(=O)Mej(CO)] [B(C6F5)(4)] (4a-d) by 2,1-insertion of L2Pd{C=O)Me}(VC)(+) intermediates to yield the O-chelated products [L2Pd-CHClCH2C(=O)Me}[B(C6F5)(4)] (5a-d). 5a-d were characterized by NMR spectroscopy, and the molecular structures of 5a and 5b.CH2Cl2 were determined by X-ray crystallography. The VC 2,1-insertion regiochemistry is favored in part because the alternative L2Pd{CH2CHClC(=O)Me}(+) 1,2-insertion products would be destabilized by placement of the electron-withdrawing Cl and acyl substituents on the same carbon. In contrast to analogous nonhalogenated L2Pd{CHRCHR'C(=O)Me}(+) species, 5a,c do not further react with CO, due to the stability of the chelate ring and the low migratory aptitude of the -CHClCH2C(=O)Me group.

  DOI：

  10.1021/om021028h
• 作为产物：
  描述：

  一氧化碳 、 四(五氟苯基)硼酸锂与乙醚的化合物 、 [((1,3-bis(diphenylphosphino)propane)Pd(Me))2(μ-Cl)][B(C6F5)4] 以 二氯甲烷-D2 为溶剂， 生成 [(1,3-bis(diphenylphosphino)propane)Pd(COMe)(CO)][B(C6F5)4]
  参考文献：
  名称：

  Reaction of Vinyl Chloride with Cationic Palladium Acyl Complexes

  摘要：

  Vinyl chloride (VC) reacts with the cationic Pd complexes [L2Pd(Me)(CO)] [B(C6F5)(4)] (3a-d; L-2 = Me(2)bipy, (t)Bu(2)bipy, dppp, dmpe) and [L2Pd{C(=O)Mej(CO)] [B(C6F5)(4)] (4a-d) by 2,1-insertion of L2Pd{C=O)Me}(VC)(+) intermediates to yield the O-chelated products [L2Pd-CHClCH2C(=O)Me}[B(C6F5)(4)] (5a-d). 5a-d were characterized by NMR spectroscopy, and the molecular structures of 5a and 5b.CH2Cl2 were determined by X-ray crystallography. The VC 2,1-insertion regiochemistry is favored in part because the alternative L2Pd{CH2CHClC(=O)Me}(+) 1,2-insertion products would be destabilized by placement of the electron-withdrawing Cl and acyl substituents on the same carbon. In contrast to analogous nonhalogenated L2Pd{CHRCHR'C(=O)Me}(+) species, 5a,c do not further react with CO, due to the stability of the chelate ring and the low migratory aptitude of the -CHClCH2C(=O)Me group.

  DOI：

  10.1021/om021028h