(η5-DMP)Mn(CO)2(η2-Bz) | 1240400-71-8

• 英文名称: (η5-DMP)Mn(CO)2(η2-Bz)
• 英文别名: (η5-2,5-dimethylpyrrole)Mn(CO)2(η2-benzene)
• CAS: 1240400-71-8
• 化学式: C₁₄H₁₄MnNO₂
• 分子量: 283.209
• InChiKey: LOIIOASOTQJKMK-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：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  四氢呋喃 、 (η5-DMP)Mn(CO)2(η2-Bz) 以 环己烷 为溶剂， 生成 (η5-DMP)Mn(CO)2(THF)
  参考文献：
  名称：

  Ligand Substitution from the (η⁵-DMP)Mn(CO)₂(Solv) [DMP = 2,5-dimethylpyrrole, Solv = solvent] Complexes: To Ring Slip or Not to Ring Slip?

  摘要：

  The mechanism and energetics of the displacement of solvent from photolytically generated (eta(5)-DMP)Mn(CO)(2)(Solv) complexes has been studied [DMP = 2,5-dimethylpyrrole, Solv = solvent]. Rate enhancement relative to the eta(5)-cyclopentadienyl (Cp) system is not observed in the displacement of weakly bound solvents. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed density functional theory (DFT) calculations. The results indicate that for both the Cp and the DMP based systems the displacement of weakly bound solvents proceeds by a dissociative or I-d mechanism. This is in sharp contrast to CO displacement from (eta(5)-DMP)Mn(CO)(3), which is known to proceed by an associative mechanism by way of an eta(3) ring slip intermediate. The associative substitution pathway only becomes competitive with the dissociative channel when the Mn-Solv bond dissociation enthalpy is more than 33 kcal/mol.

  DOI：

  10.1021/ic101123y
• 作为产物：
  描述：

  (η5-2,5-dimethylpyrrolyl)tricarbonylmanganese(I) 、 苯 以 环己烷 为溶剂， 生成 (η5-DMP)Mn(CO)2(η2-Bz)
  参考文献：
  名称：

  Ligand Substitution from the (η⁵-DMP)Mn(CO)₂(Solv) [DMP = 2,5-dimethylpyrrole, Solv = solvent] Complexes: To Ring Slip or Not to Ring Slip?

  摘要：

  The mechanism and energetics of the displacement of solvent from photolytically generated (eta(5)-DMP)Mn(CO)(2)(Solv) complexes has been studied [DMP = 2,5-dimethylpyrrole, Solv = solvent]. Rate enhancement relative to the eta(5)-cyclopentadienyl (Cp) system is not observed in the displacement of weakly bound solvents. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed density functional theory (DFT) calculations. The results indicate that for both the Cp and the DMP based systems the displacement of weakly bound solvents proceeds by a dissociative or I-d mechanism. This is in sharp contrast to CO displacement from (eta(5)-DMP)Mn(CO)(3), which is known to proceed by an associative mechanism by way of an eta(3) ring slip intermediate. The associative substitution pathway only becomes competitive with the dissociative channel when the Mn-Solv bond dissociation enthalpy is more than 33 kcal/mol.

  DOI：

  10.1021/ic101123y