1-acetyl-1'-(4-pyridyl)ferrocene | 259232-80-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-acetyl-1'-(4-pyridyl)ferrocene
• 英文别名: 1-cyclopenta-1,3-dien-1-ylethanone;4-cyclopenta-1,3-dien-1-ylpyridine;iron(2+)
• CAS: 259232-80-9
• 化学式: C₁₇H₁₅FeNO
• 分子量: 305.159
• InChiKey: QBJGTOCPDZPTJV-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：

  mono(pentaamino(hydroxy)ruthenium(VIII)) mono(hexafluorophosphate(V)) hydrate 、 1-acetyl-1'-(4-pyridyl)ferrocene 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Tuning Metal-to-Metal Charge Transfer of Mixed-Valence Complexes Containing Ferrocenylpyridine and Rutheniumammines via Solvent Donicity and Substituent Effects

  摘要：

  A homogeneous series of heterobimetallic complexes of [R-Fc(4-py)Ru(NH3)(5)](PF6)(2) (R = II, Et, Br, acetyl; Fc(4-py) = 4-ferrocenylpyridine) have been prepared and characterized. The mixed-valence species generated in situ using ferrocenium hexafluorophosphate as the oxidant show class II behavior, and the oxidized sites are ruthenium centered. Delta E-1/2, E-1/2(Fe-III/Fe-II) - E-1/2(Ru-III/Ru-II), an upper limit for Delta G degrees that is an energetic difference between the donor and acceptor sites, changes sharply and linearly with Gutmann solvent donor number (DN) and Hammett substituent constants (sigma). The solvent-dependent and substituent-dependent intervalence transfer bands were found to vary almost exclusively with Delta E-1/2. The activation energy for the optical electron transfer versus Delta E-1/2 plot yields a common nuclear reorganization energy (lambda) of 0.74 +/- 0.04 eV for this series. The equation that allows one to incorporate the effect of both solvent donicity and substituents on optical electron transfer is E-op = lambda + Delta G degrees, where Delta G degrees = (Delta G degrees)(intrinsic) + (Delta G degrees)(solvent donicity) + (Delta G degrees)(substituent effect) (Delta G degrees)(intrinsic) with a numerical value of 0.083 +/- 0.045 eV was obtained from the intercept of the Delta E-1/2 of [H-Fc(4-py)Ru(NH3)(5)](2+,3+,4+) versus DN plot. (Delta G degrees)(solvent donicity) was obtained from the average slopes of the Delta E-1/2 of [H-Fc(4-py)Ru(NH3)(5)](2+,3+,4+) versus DN plot, and (Delta G degrees)(substituent effect) was Obtained from the average slopes of the corresponding Delta E-1/2 versus a plot. The empirical equation allows one to finely tune E-op of this series to E-op = 0.82 + 0.019(DN) + 0.44 sigma eV at 298 K, and the discrepancy between the calculated and experimental data is less than 6%.

  DOI：

  10.1021/ic990839j
• 作为产物：
  描述：

  manganese(IV) oxide 、 1-ethyl-1'-(4-pyridyl)ferrocene 以 二氯甲烷 为溶剂， 以50%的产率得到1-acetyl-1'-(4-pyridyl)ferrocene
  参考文献：
  名称：

  Tuning Metal-to-Metal Charge Transfer of Mixed-Valence Complexes Containing Ferrocenylpyridine and Rutheniumammines via Solvent Donicity and Substituent Effects

  摘要：

  A homogeneous series of heterobimetallic complexes of [R-Fc(4-py)Ru(NH3)(5)](PF6)(2) (R = II, Et, Br, acetyl; Fc(4-py) = 4-ferrocenylpyridine) have been prepared and characterized. The mixed-valence species generated in situ using ferrocenium hexafluorophosphate as the oxidant show class II behavior, and the oxidized sites are ruthenium centered. Delta E-1/2, E-1/2(Fe-III/Fe-II) - E-1/2(Ru-III/Ru-II), an upper limit for Delta G degrees that is an energetic difference between the donor and acceptor sites, changes sharply and linearly with Gutmann solvent donor number (DN) and Hammett substituent constants (sigma). The solvent-dependent and substituent-dependent intervalence transfer bands were found to vary almost exclusively with Delta E-1/2. The activation energy for the optical electron transfer versus Delta E-1/2 plot yields a common nuclear reorganization energy (lambda) of 0.74 +/- 0.04 eV for this series. The equation that allows one to incorporate the effect of both solvent donicity and substituents on optical electron transfer is E-op = lambda + Delta G degrees, where Delta G degrees = (Delta G degrees)(intrinsic) + (Delta G degrees)(solvent donicity) + (Delta G degrees)(substituent effect) (Delta G degrees)(intrinsic) with a numerical value of 0.083 +/- 0.045 eV was obtained from the intercept of the Delta E-1/2 of [H-Fc(4-py)Ru(NH3)(5)](2+,3+,4+) versus DN plot. (Delta G degrees)(solvent donicity) was obtained from the average slopes of the Delta E-1/2 of [H-Fc(4-py)Ru(NH3)(5)](2+,3+,4+) versus DN plot, and (Delta G degrees)(substituent effect) was Obtained from the average slopes of the corresponding Delta E-1/2 versus a plot. The empirical equation allows one to finely tune E-op of this series to E-op = 0.82 + 0.019(DN) + 0.44 sigma eV at 298 K, and the discrepancy between the calculated and experimental data is less than 6%.

  DOI：

  10.1021/ic990839j