[Co^I(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)](tetrafluoroborate) | 1608112-01-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 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)](tetrafluoroborate)
• CAS: 1608112-01-1
• 化学式: C₁₇H₂₅CoN₅*C₂₄H₂₀B
• 分子量: 677.646
• InChiKey: VCZPCESZXYZFMW-OLSRTBRHSA-N

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：
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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)](tetrafluoroborate) 、 dimethylformamidium triflate 以 乙腈 为溶剂， 以87%的产率得到[Co^II(2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene)](tetrafluoroborate)(triflate)
  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(17),2,11,13,15-pentaene)(MeCN)](BPh₄)₂ 在 tris(bipyridine)ruthenium(II) dichloride hexahydrate 、 三乙胺 作用下， 以 乙腈 为溶剂， 生成 [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：

  通过快速扫描 FT-IR 光谱直接观察四氮杂催化剂 [CoIIN4H(MeCN)]2+将 CO2 转化为 CO 的双电子还原中间体

  摘要：

  在寻找四氮杂催化剂的双电子还原中间体 [Co(II)N4H(MeCN)](2+) (N4H = 2,12-二甲基-3,7,11,17-四氮杂双环[11.3. 1]heptadeca-1(17),2,11,13,15-pentaene) 用于 CO2 还原和导致 CO 产物形成的基本步骤，可见光敏化催化的快速扫描 FT-IR 光谱，在湿乙腈 (CD3CN) 溶液中使用 Ir(ppy)3，导致观察到两个连续的中间体。最初形成的单电子还原的 [Co(I)N4H](+)-CO2 加合物被第二个电子转化为瞬态 [Co(I)N4H](+)-CO2(-) 复合物，该复合物自发地转化了 CO2在催化剂再生（室温）下，在黑暗中，在第二个时间尺度的限速步骤中转化为 CO。[Co(I)N4H](+)-CO2(-) 配合物和前面的单电子 [Co(I)N4H](+)-CO2 中间体的大环红外光谱显示出非常相似但在羧

  DOI：

  10.1021/jacs.6b05248