cis-{Ru(III)(2,2'-bipyridine)2(pyridine)(OH)}(ClO4)2 | 75495-10-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: cis-{Ru(III)(2,2'-bipyridine)2(pyridine)(OH)}(ClO4)2
• 英文别名: cis-[Ru(III)(2,2'-bipyridine)2(pyridine)(OH)](ClO4)2
• CAS: 75495-10-2
• 化学式: C₂₅H₂₂N₅ORu*2ClO₄
• 分子量: 708.454
• InChiKey: MJUKJFYOJGSLCT-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  [Ru(bpy)2(py)OH2](ClO4)2*H2O 以 further solvent(s) 为溶剂， 以56%的产率得到cis-{Ru(III)(2,2'-bipyridine)2(pyridine)(OH)}(ClO4)2
  参考文献：
  名称：

  Moyer, Bruce A.; Meyer, Thomas J., Inorganic Chemistry, 1981, vol. 20, # 2, p. 436 - 444

  摘要：

  DOI：

文献信息

• Stepwise Oxidation of Anilines by <i>cis</i>-[Ru^IV(bpy)₂(py)(O)]²⁺
  作者：Won K. Seok、Thomas J. Meyer

  DOI：10.1021/ic0302985

  日期：2004.8.1

  The net six-electron oxidation of aniline to nitrobenzene or azoxybenzene by cis-[Ru-IV(bpy)(2)(py)(O)](2+) (bpy is 2,2'-bipyricline; py is pyridine) occurs in a series of discrete stages. In the first, initial two-electron oxidation is followed by competition between oxidative coupling with aniline to give 1,2-diphenylhydrazine and capture by H2O to give N-phenylhydroxylamine. The kinetics are first order in aniline and first order in Ru(IV) with k(25.1 degreesC, CH3CN) = (2.05 +/- 0.18) x 10(2) M-1 s(-1) (DeltaH(double dagger) = 5.0 +/- 0.7 kcal/mol; DeltaS(double dagger) = -31 +/- 2 eu). On the basis of competition experiments, k(H2O)/k(D2O) kinetic isotope effects, and the results of an O-18 labeling study, it is concluded that the initial redox step probably involves proton-coupled two-electron transfer from aniline to cis-[Ru-IV(bpy)(2)(py)(O)](2+) (Ru-IV=O2+). The product is an intermediate nitrene (PhN) or a protonated nitrene (PhNH+) which is captured by water to give PhNHOH or aniline to give PhNHNHPh. In the following stages, PhNHOH, once formed, is rapidly oxidized by Ru-IV=O2+ to PhNO and PhNHNHPh to PhN=NPh. The rate laws for these reactions are first order in Ru-I =O2+ and first order in reductant with k(14.4 degreesC, H2O/(CH3)(2)CO) = (4.35 +/- 0.24) x 10(6) M-1 s(-1) for PhNHOH and k(25.1 degreesC, CH3CN) = (1.79 +/- 0.14) x 10(4) M-1 s(-1) for PhNHNHPh. In the final stages of the six-electron reactions, PhNO is oxidized to PhNO2 and PhN=NPh to PhN(O)=NPh. The oxidation of PhNO is first order in PhNO and in Ru-IV=O2+ with k(25.1 degreesC, CH3CN) = 6.32 +/- 0.33 M-1 s(-1) (DeltaH(double dagger) = 4.6 +/- 0.8 kcal/mol; DeltaS(double dagger) = -39 +/- 3 eu). The reaction occurs by O-atom transfer, as shown by an O-18 labeling study and by the appearance of a nitrobenzenebound intermediate at low temperature.