[Rh(bis(2-pyridylcarbonyl)amide)2][ClO4] | 215370-44-8

• 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: [Rh(bis(2-pyridylcarbonyl)amide)2][ClO4]
• CAS: 215370-44-8
• 化学式: C₂₄H₁₆N₆O₄Rh*ClO₄
• 分子量: 654.785
• InChiKey: PPEUYCLBWWDBGI-UHFFFAOYSA-K

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：

  2,4,6-三(2-吡啶基)三嗪 以 乙醇 、 水 、 丙酮 为溶剂， 生成 [Rh(bis(2-pyridylcarbonyl)amide)2][ClO4]
  参考文献：
  名称：

  Synthesis and Characterization of Rhodium Complexes Containing 2,4,6-Tris(2-pyridyl)-1,3,5-triazine and Its Metal-Promoted Hydrolytic Products: Potential Uses of the New Complexes in Electrocatalytic Reduction of Carbon Dioxide

  摘要：

  The reaction of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with RhCl3. 3H(2)O has been studied under different experimental conditions. This reaction in ethanol resulted in the formation of [Rh(tptz)Cl-3]. 2H(2)O (1), whereas the bis-chelate complex [Rh(tptz)(2)][ClO4](3). 2H(2)O (2) was obtained in a two-step reaction in acetone; the chlorides from RhCl3 were removed in the first step using AgClO4, and the ligand tptz was added in the second step. Complexes 1 and 2, when refluxed in ethanol-water (1:1), resulted in metal-promoted hydrolysis of tptz to bis(2-pyridylcarbonyl)amide anion (bpca) and 2-picolinamide (pa), yielding the complexes [Rh(bpca)(pa)Cl][PF6]. H2O (3) and [Rh(bpca)(2)][ClO4] (6), respectively. A mixed-ligand complex, [Rh(bpca)(tpy)][PF6](2). CH3CN (4), was obtained by the reaction of either 1 with tpy or [Rh(tpy)Cl-3] (5) with tptz in ethanol-water medium. The crystal structures of complexes 1 and 4 have been determined. Crystal data: complex 1, monoclinic, P2(1)/c, a 11.642(2) Angstrom, b = 7.302(2) Angstrom, c = 24.332(3) Angstrom, beta = 96.420(10)degrees, Z = 4, R = 0.040, and wR2 = 0.117; complex 4, triclinic, P (1) over bar, a = 9.581(1) Angstrom, b = 12.933(2) Angstrom, c = 14.493(2) Angstrom, alpha = 82.480(10)degrees, beta = 71.810(10)degrees, gamma = 75.100(10)degrees, Z = 2, R = 0.030, and wR2 = 0.082. The two water molecules of complex 1 make short contacts with the carbon atoms adjacent to the metal-bound nitrogen atom of the triazine ring; this observation provides some insight about the "intermediate" of the hydrolysis. X-ray and NMR data suggest that the electron-withdrawing effect of the metal ion is the major responsible factor for the hydrolysis of tptz. The cyclic voltammograms of the complexes exhibit a metal-based 2e reduction (Rh(III) --> Rh(I)) at the potential range -0.42 to -0.98 V vs SCE, followed by ligand-based redox couple(s). These novel complexes show effective catalytic properties for the electrocatalytic reduction of carbon dioxide in the potential range -1.26 to -1.44 V.

  DOI：

  10.1021/ic9709739