[Co^I(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(-1H)] | 53294-83-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [Co^I(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(-1H)]
• CAS: 53294-83-0
• 化学式: C₁₅H₂₁CoN₄
• 分子量: 316.352
• InChiKey: YKXURJUJZFPWAD-RFEQIDDFSA-N

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^I(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)(-1H)] 、 四苯硼钠 、 乙腈 以 水 为溶剂， 以65%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)](tetrafluoroborate)
  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：

  [Co^II(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)](tetrafluoroborate)2 在 potassium graphite 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 [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