[1,2-bis[4,5-dihydro-3H-dibenzo[c-e]azepino]ethane](η3-cyclohexenyl)palladium hexafluorophosphate | 1009811-12-4

• 英文名称: [1,2-bis[4,5-dihydro-3H-dibenzo[c-e]azepino]ethane](η3-cyclohexenyl)palladium hexafluorophosphate
• CAS: 1009811-12-4
• 化学式: C₃₆H₃₇N₂Pd*F₆P
• 分子量: 749.087
• InChiKey: UJZATOPCKQFYCR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  cinchonidinium Δ-tris(tetrachlorocatecholato)phosphate 、 [1,2-bis[4,5-dihydro-3H-dibenzo[c-e]azepino]ethane](η3-cyclohexenyl)palladium hexafluorophosphate 生成 [1,2-bis[4,5-dihydro-3H-dibenzo[c-e]azepino]ethane](η3-cyclohexenyl)palladium rac-tris(tetrachlorocatecholato)phosphate
  参考文献：
  名称：

  Self-Adaptable Catalysts:  Substrate-Dependent Ligand Configuration

  摘要：

  Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5dihydro-3H-dibenzo[c-e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic alkylations. According to NMR and DFT studies, the ligand prefers C-s conformation in both eta(3)-1,3-diphenylpropenyl and eta(3)-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different conformations in complexes derived from the two types of allyl systems in both solution and, as verified by X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of adapting its structure to the reacting substrate. The different structural preferences also provide an explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed allylic alkylations using pseudo-C-2 and pseudo-C-s symmetric ligands.

  DOI：

  10.1021/ja074044k
• 作为产物：
  描述：

  六氟磷酸银 、 bis(μ-chloro)bis[(1,2,3-η)-cyclohexenyl]dipalladium 、 1,2-bis-[(R)-4,5-dihydro-3H-dinaphtho[1,2-C:2',1'-e]azepino]ethane 以 二氯甲烷 为溶剂， 以31%的产率得到[1,2-bis[4,5-dihydro-3H-dibenzo[c-e]azepino]ethane](η3-cyclohexenyl)palladium hexafluorophosphate
  参考文献：
  名称：

  Self-Adaptable Catalysts:  Substrate-Dependent Ligand Configuration

  摘要：

  Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5dihydro-3H-dibenzo[c-e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic alkylations. According to NMR and DFT studies, the ligand prefers C-s conformation in both eta(3)-1,3-diphenylpropenyl and eta(3)-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different conformations in complexes derived from the two types of allyl systems in both solution and, as verified by X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of adapting its structure to the reacting substrate. The different structural preferences also provide an explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed allylic alkylations using pseudo-C-2 and pseudo-C-s symmetric ligands.

  DOI：

  10.1021/ja074044k