[(R/SRu, Spl)-RuCp(2-(1-N,N-dimethylaminomethyl)-1-diphenylphosphino ferrocene)(CO)]PF6 | 247195-97-7

• 英文名称: [(R/SRu, Spl)-RuCp(2-(1-N,N-dimethylaminomethyl)-1-diphenylphosphino ferrocene)(CO)]PF6
• CAS: 247195-97-7
• 化学式: C₃₁H₃₁FeNOPRu*F₆P
• 分子量: 766.448
• InChiKey: FVMXXFDYTKSWQT-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：

  [(R/SRu, Spl)-RuCp(2-(1-N,N-dimethylaminomethyl)-1-diphenylphosphino ferrocene)(CO)]PF6 、 一氧化碳 以 二氯甲烷 为溶剂， 以95%的产率得到[(R/SRu, RC, Spl)-RuCp(2-(1-N,N-diethylaminoethyl)-1-diphenylphosphino ferrocene)(CO)]PF6
  参考文献：
  名称：

  Thermodynamically Controlled Formation of Diastereopure Three-Legged Piano-Stool Complexes. The Substitution Chemistry of [RuCp(aminophosphinoferrocene)(CH₃CN)]PF₆

  摘要：

  Treatment of [RuCp(CH3CN)(3)](+) with the chiral ligands PN* = (R-c,S-pl)-2-(1-N,N-dimethylaminoethyl)-1-diphenylphosphinoferrocene, (S-pl)-2-(1-N,N-dimethylaminomethyl)-1-diphenylphosphinoferrocene, and (R-c,S-pl)-2-(1-N,N-diethylaminoethyl)-1-diphenylphosphinoferrocene affords diastereoselectively the labile cationic complexes [(S-Ru)-RuCp(PN*)(CH3CN)](+). The exchange kinetics of CH3CN has been studied as a function of temperature, revealing a dissociative mechanism, and therefore thermodynamic control is responsible for the diastereoselective formation of [(S-Ru)-RuCp(PN*)(CH3CN)](+). These react with HC=CPh to give the chiral vinylidene complexes [(R-Ru)-RuCp(PN*)(=C=CHPh)](+) in highly diastereoselective fashion. With CO complexes [RuCp(PN*)(CO)](+) are obtained in high yields but with significantly decreased stereoselectivity due to kinetic control of the substitution reaction. Under photochemical conditions epimerization occurs to give [(R-Ru)-RuCp(PN*)-(CO)](+) with a de of > 98%. In the case of [RuCp((R-c,S-pl)-2-(1-N,N-diethylaminoethyl)- 1-diphenylphosphinoferrocene)(CO)](+) the diastereomeric excess increases from 87 to >98% upon heating due to an intramolecular epimerization. The absolute configuration of representative complexes has been determined by X-ray crystallography.

  DOI：

  10.1021/om990307a
• 作为产物：
  描述：

  [(SRu, Spl)-RuCp(2-(1-N,N-dimethylaminomethyl)-1-diphenylphosphino ferrocene)(CH3CN)]PF6 、 一氧化碳 以 二氯甲烷 为溶剂， 以93%的产率得到[(R/SRu, Spl)-RuCp(2-(1-N,N-dimethylaminomethyl)-1-diphenylphosphino ferrocene)(CO)]PF6
  参考文献：
  名称：

  Thermodynamically Controlled Formation of Diastereopure Three-Legged Piano-Stool Complexes. The Substitution Chemistry of [RuCp(aminophosphinoferrocene)(CH₃CN)]PF₆

  摘要：

  Treatment of [RuCp(CH3CN)(3)](+) with the chiral ligands PN* = (R-c,S-pl)-2-(1-N,N-dimethylaminoethyl)-1-diphenylphosphinoferrocene, (S-pl)-2-(1-N,N-dimethylaminomethyl)-1-diphenylphosphinoferrocene, and (R-c,S-pl)-2-(1-N,N-diethylaminoethyl)-1-diphenylphosphinoferrocene affords diastereoselectively the labile cationic complexes [(S-Ru)-RuCp(PN*)(CH3CN)](+). The exchange kinetics of CH3CN has been studied as a function of temperature, revealing a dissociative mechanism, and therefore thermodynamic control is responsible for the diastereoselective formation of [(S-Ru)-RuCp(PN*)(CH3CN)](+). These react with HC=CPh to give the chiral vinylidene complexes [(R-Ru)-RuCp(PN*)(=C=CHPh)](+) in highly diastereoselective fashion. With CO complexes [RuCp(PN*)(CO)](+) are obtained in high yields but with significantly decreased stereoselectivity due to kinetic control of the substitution reaction. Under photochemical conditions epimerization occurs to give [(R-Ru)-RuCp(PN*)-(CO)](+) with a de of > 98%. In the case of [RuCp((R-c,S-pl)-2-(1-N,N-diethylaminoethyl)- 1-diphenylphosphinoferrocene)(CO)](+) the diastereomeric excess increases from 87 to >98% upon heating due to an intramolecular epimerization. The absolute configuration of representative complexes has been determined by X-ray crystallography.

  DOI：

  10.1021/om990307a