[Ru(η5-C5,κ-P-C5H4CH2CH2N(Me)PO2C12H8)(acetonitrile)2]PF6 | 1225022-45-6

• 英文名称: [Ru(η5-C5,κ-P-C5H4CH2CH2N(Me)PO2C12H8)(acetonitrile)2]PF6
• CAS: 1225022-45-6
• 化学式: C₂₄H₂₅N₃O₂PRu*F₆P
• 分子量: 664.489
• InChiKey: SFUSPGXIHSMWQL-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

• 作为产物：
  描述：

  [Ru(η5-C5H4CH2CH2N(Me)PO2C12H8)(η6-p-cymene)]PF6 、 乙腈 在 biphenyl 作用下， 以 乙腈 为溶剂， 以40%的产率得到[Ru(η5-C5,κ-P-C5H4CH2CH2N(Me)PO2C12H8)(acetonitrile)2]PF6
  参考文献：
  名称：

  Redox Isomerization of Allylic Alcohols Catalyzed by Osmium and Ruthenium Complexes Containing a Cyclopentadienyl Ligand with a Pendant Amine or Phosphoramidite Group: X-ray Structure of an η³-1-Hydroxyallyl-Metal-Hydride Intermediate

  摘要：

  Complexes [MCl2(eta(6)-p-cymene)](2) (M = Os (1a), Ru (1b)) react with Li(C5H4CH2CH2NHMe) (LiCpN) and KPF6 to give the sandwich derivatives [M(eta(5)-Cp-N)(eta(6)-p-cymene)]PF6 (M = Os (2a), Ru (2b)). Treatment of 2a and 2b with (2,2'-biphenol)PCI leads to [M(eta(5)-Cp-P)(eta(6)-p-cymene)]PF6 (M = Os (3a), Ru (3b); CpP = C5H4CH2CH2N(Me)P(2,2'-biphenol)). The photolysis of 2a, 2b, 3a, and 3h in acetonitrile produces the release of the p-cymene group and the coordination of the cyclopentadienyl pendant substituent to the metal center to afford [M(eta(5)-C-5,kappa-N-CpN)(CH3CN)(2)]PF6 (M = Os (4a), Ru (4b)) and [M(eta(5)-C-5,kappa-P-Cp-P)(CH3CN)(2)]PF6 (M = Os (5a), Ru (5b)). Complex 4a, which has been characterized by X-ray diffraction analysis, is a more efficient catalyst precursor than 4b for the redox isomerization of primary allylic alcohols, while the latter is more efficient than the former for the redox isomerization of secondary allylic alcohols. From the catalytic solutions containing 4a and 2-methyl-2-propen-1-ol, the eta 3-1-hydroxyallyl complex [OsH(eta(5)-C-5,kappa-N-CPN){eta(3)-CH2C(CH3)CHOH}]PF6 (6) has been crystallized and characterized by spectroscopic methods and X-ray diffraction analysis. The structure shows a N-H center dot center dot center dot O hydrogen bond (2.22 A) between the NH-hydrogen atom of the coordinated pendant amine group and the oxygen atom of the hydroxy substituent of the allyl ligand.

  DOI：

  10.1021/om100126t