[Co^II(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2] | 22955-47-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: [Co^II(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2]
• 英文别名: [Co^II(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)]Br
• CAS: 22955-47-1；67270-35-3
• 化学式: C₁₅H₂₂Br₂CoN₄
• 分子量: 477.168
• InChiKey: JJVLZWZAAKXZBR-RTABLGJVSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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：

  [Co^II(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2] 在 potassium graphite 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以83%的产率得到[Co^I(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(-1H)]
  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
• 作为产物：
  描述：

  3,3'-二氨基二丙基胺 、 2,6-二乙酰基吡啶 、 cobalt(II) bromide 以 乙醇 为溶剂， 生成 [Co^II(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(Br)2]
  参考文献：
  名称：

  通过同时调节三种取代基效应来提高分子电催化剂的 CO2 还原活性

  摘要：

  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

  DOI：

  10.1021/jacs.0c09357