(NC)5Fe(4-cyanopyridine)Ru(NH3)5(1-) | 184647-04-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: (NC)5Fe(4-cyanopyridine)Ru(NH3)5(1-)
• CAS: 184647-04-9
• 化学式: C₁₁H₁₉FeN₁₂Ru
• 分子量: 476.269
• InChiKey: FIDOGECNDFGBFK-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  (NC)5Fe(4-cyanopyridine)Ru(NH3)5(1-) 在 dipotassium peroxodisulfate 作用下， 以 水 为溶剂， 生成 (NC)5Fe(4-cyanopyridine)Ru(NH3)5
  参考文献：
  名称：

  Mixed-Valence Cyanopyridine-Bridged Complexes of Pentacyanoferrate and Pentaammineruthenium:  Electronic Structure, Stability, and Redox Reactivity

  摘要：

  The mixed-valence binuclear complexes, [(NC)(5)Fe(pyCN)Ru(NH3)(5)](n) (4- and 3-cyanopyridine isomers, with nitrile-N and pyridine-N binding to Ru and Fe, respectively) were prepared as solid compounds through stoichiometric oxidation of the fully reduced (II,II) binuclear complexes, R, with peroxydisulfate. By analysis of IR spectra, the solids were observed to be a mixture of the predominant electronic isomers with a Fe-II, Ru-III distribution, with minor amounts of the Fe-III, Ru-II isomers. In aqueous solution, R was oxidized with peroxydisulfate to M, the mixed-valence complex, and to Ox, the fully oxidized complex. The M complex shows an intervalence band at 938 nm; by application of the Hush model, it is described as a valence-trapped Ru-II, Fe-III complex: the latter electronic distribution is supported by UV-visible, electrochemical, and kinetic data, but a minor amount of the isomer with a Fe-II, Ru-III distribution is also present in the equilibrium. The M complex is unstable toward dissociation and further outer-sphere reactions, leading to hydrolyzed products in the time scale of minutes. Hydrolysis is also the main decomposition route of the Ox complex. In the reactions with excess peroxydisulfate, the analysis of successive spectra allows the elucidation of the rate constants for the one-electron processes leading to M and Ox. The rate constants for the formation and dissociation of M, as well as for the hydrolysis of Ox, were also obtained. A kinetic control is operative in the oxidation reactions, with a preferential attack of peroxydisulfate on the more reactive Ru(II) center. The role of electronic isomerization is discussed in the overall kinetic scheme, and the rate constant values for oxidation agree with predictions based on Marcus LFER, in accord with data published for related complexes.

  DOI：

  10.1021/ic960489q
• 作为产物：
  描述：

  sodium amminepentacyanoferrate(II) trihydrate 、 [Ru(NH3)5(4-cyanopyridine)](PF6)2 以 水 为溶剂， 生成 (NC)5Fe(4-cyanopyridine)Ru(NH3)5(1-)
  参考文献：
  名称：

  Mixed-Valence Cyanopyridine-Bridged Complexes of Pentacyanoferrate and Pentaammineruthenium:  Electronic Structure, Stability, and Redox Reactivity

  摘要：

  The mixed-valence binuclear complexes, [(NC)(5)Fe(pyCN)Ru(NH3)(5)](n) (4- and 3-cyanopyridine isomers, with nitrile-N and pyridine-N binding to Ru and Fe, respectively) were prepared as solid compounds through stoichiometric oxidation of the fully reduced (II,II) binuclear complexes, R, with peroxydisulfate. By analysis of IR spectra, the solids were observed to be a mixture of the predominant electronic isomers with a Fe-II, Ru-III distribution, with minor amounts of the Fe-III, Ru-II isomers. In aqueous solution, R was oxidized with peroxydisulfate to M, the mixed-valence complex, and to Ox, the fully oxidized complex. The M complex shows an intervalence band at 938 nm; by application of the Hush model, it is described as a valence-trapped Ru-II, Fe-III complex: the latter electronic distribution is supported by UV-visible, electrochemical, and kinetic data, but a minor amount of the isomer with a Fe-II, Ru-III distribution is also present in the equilibrium. The M complex is unstable toward dissociation and further outer-sphere reactions, leading to hydrolyzed products in the time scale of minutes. Hydrolysis is also the main decomposition route of the Ox complex. In the reactions with excess peroxydisulfate, the analysis of successive spectra allows the elucidation of the rate constants for the one-electron processes leading to M and Ox. The rate constants for the formation and dissociation of M, as well as for the hydrolysis of Ox, were also obtained. A kinetic control is operative in the oxidation reactions, with a preferential attack of peroxydisulfate on the more reactive Ru(II) center. The role of electronic isomerization is discussed in the overall kinetic scheme, and the rate constant values for oxidation agree with predictions based on Marcus LFER, in accord with data published for related complexes.

  DOI：

  10.1021/ic960489q