{tetrakis(4-chlorophenyl)cyclopentadienone}tricarbonylruthenium(0) | 135853-92-8

• 英文名称: {tetrakis(4-chlorophenyl)cyclopentadienone}tricarbonylruthenium(0)
• CAS: 135853-92-8
• 化学式: C₃₂H₁₆Cl₄O₄Ru
• 分子量: 707.359
• InChiKey: XLOISMZVEBBEGH-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：
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• sp3杂化的碳原子比例：
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• 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：

  {tetrakis(4-chlorophenyl)cyclopentadienone}tricarbonylruthenium(0) 在 sodium carbonate 作用下， 以 丙酮 为溶剂， 以79%的产率得到{(4-Cl-C6H4)4C4CO}2H(μ-H)(CO)4Ru2
  参考文献：
  名称：

  Catalytic disproportionation of aldehydes with ruthenium complexes

  摘要：

  It was discovered that the ruthenium complex [(C4Ph4COHOCC4Ph4)(mu-H)][(CO)4Ru2] (2), as well as other isostructural Ru complexes, in the presence of a catalytic amount of formic acid, catalyzes the homogeneous bimolecular disproportionation reaction of aldehydes to give esters: 2RCHO --> RCOOCH2R. The reaction was found to be general and compatible with a variety of aliphatic and aromatic aldehydes and can be carried out in the presence or absence of solvent under mild conditions. It is characterized by an excellent efficiency with an initial turnover frequency reaching 5000 h-1, a measured overall turnover number of ca. 20 000, and high conversion, yield, and selectivity. Increasing the electron density on the metal and the ligand was found to accelerate the reaction. Kinetic studies indicate that the rate = k[catalyst]1/2[aldehyde]. The rate also depends on the initial formic acid concentration. A stoichiometric reaction of complex 2 with formic acid, monitored by infrared spectroscopy, shed light on the identity of the active catalytic species. No kinetic isotope effect could be detected by using PhCDO and DCOOD as reactants. Consequently, a mechanism and a detailed catalytic cycle for the bimolecular transformation of aldehydes to esters were proposed.

  DOI：

  10.1021/om00057a019
• 作为产物：
  描述：

  十二羰基三钌 、 1-氯-4-[2-(4-氯苯基)乙炔基]苯 以 甲苯 为溶剂， 以40%的产率得到{tetrakis(4-chlorophenyl)cyclopentadienone}tricarbonylruthenium(0)
  参考文献：
  名称：

  Catalytic disproportionation of aldehydes with ruthenium complexes

  摘要：

  It was discovered that the ruthenium complex [(C4Ph4COHOCC4Ph4)(mu-H)][(CO)4Ru2] (2), as well as other isostructural Ru complexes, in the presence of a catalytic amount of formic acid, catalyzes the homogeneous bimolecular disproportionation reaction of aldehydes to give esters: 2RCHO --> RCOOCH2R. The reaction was found to be general and compatible with a variety of aliphatic and aromatic aldehydes and can be carried out in the presence or absence of solvent under mild conditions. It is characterized by an excellent efficiency with an initial turnover frequency reaching 5000 h-1, a measured overall turnover number of ca. 20 000, and high conversion, yield, and selectivity. Increasing the electron density on the metal and the ligand was found to accelerate the reaction. Kinetic studies indicate that the rate = k[catalyst]1/2[aldehyde]. The rate also depends on the initial formic acid concentration. A stoichiometric reaction of complex 2 with formic acid, monitored by infrared spectroscopy, shed light on the identity of the active catalytic species. No kinetic isotope effect could be detected by using PhCDO and DCOOD as reactants. Consequently, a mechanism and a detailed catalytic cycle for the bimolecular transformation of aldehydes to esters were proposed.

  DOI：

  10.1021/om00057a019