[Co^III(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2]Br | 54891-30-4

• 英文名称: [Co^III(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2]Br
• 英文别名: [Co(CR)Br2]Br
• CAS: 54891-30-4
• 化学式: Br*C₁₅H₂₂Br₂CoN₄
• 分子量: 557.072
• InChiKey: MXPKNDWALFAYKX-UXJFZDSNSA-K

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：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  高氯酸 、 [Co^III(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2]Br 、 水 在 AgNO₃ 作用下， 以 水 为溶剂， 生成 [Co(CR)(OH2)2](ClO4)3
  参考文献：
  名称：

  Electrocatalytic Hydrogen Evolution in Acidic Water with Molecular Cobalt Tetraazamacrocycles

  摘要：

  A series of water-soluble molecular cobalt complexes of tetraazamacrocyclic ligands are reported for the electrocatalytic production of H-2 from pH 2.2 aqueous solutions. The comparative data reported for this family of complexes shed light on their relative efficiencies for hydrogen evolution in water. Rotating disk electrode voltammetry data are presented for each of the complexes discussed, as are data concerning their respective pH-dependent electrocatalytic activity. In particular, two difinine-dioxline complexes were identified as exhibiting catalytic onset at comparatively low overpotentials relative to other reported homogeneous cobalt and nickel electrocatalysts in aqueous solution. These complexes are stable at pH 2.2 and produce hydrogen with high Faradaic efficiency in bulk electrolysis experiments over time intervals ranging from 2 to 24 h.

  DOI：

  10.1021/ja210661k
• 作为产物：
  描述：

  [Co^II(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2] 、 氢溴酸 生成 [Co^III(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2]Br
  参考文献：
  名称：

  Studies of Cobalt-Mediated Electrocatalytic CO₂ Reduction Using a Redox-Active Ligand

  摘要：

  The cobalt complex [(CoN4H)-N-III(Br)(2)](+) (N4H = 2,12-dimethyl-3,7,11,17 -tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene) was used for electrocatalytic CO2 reduction in wet MeCN with a glassy carbon working electrode. When water was employed as the proton source (10 M in MeCN), CO was produced (f(CO) = 45% +/- 6.4) near the Co-1/0 redox couple for [(CoN4H)-N-III(Br)(2)](+) (E-1/2 = -1.88 V FeCp2+/0) with simultaneous H-2 evolution (f(H2) = 30% +/- 7.8). Moreover, we successfully demonstrated that the catalytically active species is homogeneous through the use of control experiments and XPS studies of the working glassy-carbon electrodes. As determined by cyclic voltammetry, CO2 catalysis occurred near the formal Co-1/0 redox couple, and attempts were made to isolate the triply reduced compound ("[(CoN4H)-N-0]"). Instead, the doubly reduced ("Co-1") compounds [CoN4] and [CoN4H(MeCN)](+) were isolated and characterized by X-ray crystallography. Their molecular structures prompted DFT studies to illuminate details regarding their electronic structure. The results indicate that reducing equivalents are stored on the ligand, implicating redox noninnocence in the ligands for H-2 evolution and CO2 reduction electrocatalysis.

  DOI：

  10.1021/ic403122j
• 作为试剂：
  描述：

  水 、 sodium nitrite 在 [Co^III(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2]Br 、 potassium chloride 作用下， 反应 1.0h， 生成 氨
  参考文献：
  名称：

  氧化还原活性钴大环络合物电催化还原氮氧阴离子

  摘要：

  钴络合物 [Co(CR)Br 2 ] +，其中 CR 是具有氧化还原活性的大环 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(17) ,2,11,13,15-戊烯已被研究用于电催化还原含水 NO 2 -和 NO 3 -。在中性 pH 值下，溴化物配体水解，提供 [Co(CR)(OH 2 )(OH)] 2+作为水溶液中的主要物质。在亚硝酸盐存在下，[Co(CR)(NO 2 ) 2 ] +作为溶液中的主要物质形成，是 NO 2 –电催化还原的前体，它被选择性地转化为具有高法拉第效率的铵。均相和多相电催化都有证据。尽管没有观察到类似的 NO 3结合，但也发生了电催化还原为铵，尽管法拉第效率较低。在这种情况下，NO 2 -作为 NO 3 -还原的中间产物生成。

  DOI：

  10.1021/acs.inorgchem.2c00199

文献信息

• Enhancing a Molecular Electrocatalyst’s Activity for CO₂Reduction by Simultaneously Modulating Three Substituent Effects
  作者：Weixuan Nie、Drew E. Tarnopol、Charles C. L. McCrory

  DOI：10.1021/jacs.0c09357

  日期：2021.3.17

  inverse scaling relationship for CO2 reduction—the maximum activity of the resulting catalysts increases as the onset potentials are driven positive due to the ligand electronic substituent effects. Incorporating all three effects simultaneously into the catalyst structure results in a Co complex [Co(PDI-PyCH3+I–)] with dramatically enhanced activity for CO2 reduction, operating with over an order of magnitude

  通过逐步整合三种协同取代基效应：扩展共轭、吸电子能力和分子内静电效应，Co 与基于吡啶基二亚胺的配体的配合物大大提高了 CO 2还原的电催化活性。将这些效应逐步结合到催化剂结构中会产生一系列配合物，这些配合物显示出 CO 2还原的非典型反比例关系——由于配体电子取代基效应，随着起始电位被驱动为正，所得催化剂的最大活性增加. 将所有三种效应同时结合到催化剂结构中会产生 Co 络合物 [Co(PDI-PyCH 3 + I –)] 具有显着增强的 CO 2还原活性，以高出一个数量级的活性（TOF cat = 4.1 × 10 4 s –1）和~0.2 V 更高的正催化起始（E onset = -1.52 V vs Fc + /0 ) 与母体复合物相比，内在活性参数 TOF 0 = 6.3 × 10 –3 s –1和 >95% 的法拉第效率，用于在 11 M 水的乙腈中生产 CO。这使得 [Co(PDI-PyCH