[2,5-Ph2-3,4-Tol2(η4-C4CO)](CO)2Ru(isopropylamine) | 431906-20-6

• 英文名称: [2,5-Ph2-3,4-Tol2(η4-C4CO)](CO)2Ru(isopropylamine)
• CAS: 431906-20-6
• 化学式: C₃₆H₃₃NO₃Ru
• 分子量: 628.733
• InChiKey: GLVYEGCJXPPOJM-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：

  [2,5-Ph2-3,4-Tol2(η4-C4CO)](CO)2Ru(isopropylamine) 、 三苯基膦 以 氘代甲苯 为溶剂， 生成 [2,5-Ph2-3,4-Tol2(η4-C4CO)]Ru(CO)2PPh3
  参考文献：
  名称：

  Reduction of Imines by Hydroxycyclopentadienyl Ruthenium Hydride:  Intramolecular Trapping Evidence for Hydride and Proton Transfer Outside the Coordination Sphere of the Metal

  摘要：

  Reduction of imines by [2,5-Ph-2-3,4-Tol(2)(eta(5)-C4COH)]Ru(CO)H-2 (2) produces kinetically stable ruthenium amine complexes. Reduction of an imine by 2 in the presence of an external amine trap gives only the complex of the newly generated amine. Reaction of 2 with H2N-p-C6H4N=CHPh (11), which contains an intramolecular amine trap, gave a 1:1 mixture of [2,5-Ph-2-3,4-Tol(2)(eta(4)-C4CO)](CO)(2)RuNH(CH2Ph)(C6H4-p-NH2) (8), formed by coordination of the newly generated amine to the ruthenium center, and [2,5-Ph-2-3,4-Tol(2)(eta(4)-C4CO)](CO)(2)RuNH2C6H4-p-NHCH2Ph (9), formed by coordination of the amine already present in the substrate. These results require transfer of hydrogen to the imine outside the coordination sphere of the metal to give a coordinatively unsaturated intermediate that can be trapped inside the initial solvent cage. Amine diffusion from the solvent cage must be much slower than coordination to the metal center. Mechanisms requiring prior coordination of the substrate to ruthenium would have led only to 8 and can be eliminated.

  DOI：

  10.1021/ja053956o
• 作为产物：
  描述：

  [[2,5-Ph2-3,4-Tol2-(η4-C4CO)]Ru(CO)2]2 、 异丙胺 以 二氯甲烷-D2 为溶剂， 生成 [2,5-Ph2-3,4-Tol2(η4-C4CO)](CO)2Ru(isopropylamine)
  参考文献：
  名称：

  Reduction of Imines by Hydroxycyclopentadienyl Ruthenium Hydride:  Intramolecular Trapping Evidence for Hydride and Proton Transfer Outside the Coordination Sphere of the Metal

  摘要：

  Reduction of imines by [2,5-Ph-2-3,4-Tol(2)(eta(5)-C4COH)]Ru(CO)H-2 (2) produces kinetically stable ruthenium amine complexes. Reduction of an imine by 2 in the presence of an external amine trap gives only the complex of the newly generated amine. Reaction of 2 with H2N-p-C6H4N=CHPh (11), which contains an intramolecular amine trap, gave a 1:1 mixture of [2,5-Ph-2-3,4-Tol(2)(eta(4)-C4CO)](CO)(2)RuNH(CH2Ph)(C6H4-p-NH2) (8), formed by coordination of the newly generated amine to the ruthenium center, and [2,5-Ph-2-3,4-Tol(2)(eta(4)-C4CO)](CO)(2)RuNH2C6H4-p-NHCH2Ph (9), formed by coordination of the amine already present in the substrate. These results require transfer of hydrogen to the imine outside the coordination sphere of the metal to give a coordinatively unsaturated intermediate that can be trapped inside the initial solvent cage. Amine diffusion from the solvent cage must be much slower than coordination to the metal center. Mechanisms requiring prior coordination of the substrate to ruthenium would have led only to 8 and can be eliminated.

  DOI：

  10.1021/ja053956o