Na[(difluoroboryldiphenylglyoxime)2Co(acetonitrile)] | 946599-19-5

• 英文名称: Na[(difluoroboryldiphenylglyoxime)2Co(acetonitrile)]
• CAS: 946599-19-5
• 化学式: C₃₀H₂₃B₂CoF₄N₅O₄*Na
• 分子量: 697.142
• InChiKey: RXEJKLQAYNDWDQ-NIULTXFDSA-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：

  12-冠醚-4 、 Na[(difluoroboryldiphenylglyoxime)2Co(acetonitrile)] 以 乙醚 、 乙腈 为溶剂， 生成 Na(12-crown-4)2[(difluoroboryldiphenylglyoxime)2Co(acetonitrile)]*Et2O*CH3CN
  参考文献：
  名称：

  Electrocatalytic Hydrogen Evolution at Low Overpotentials by Cobalt Macrocyclic Glyoxime and Tetraimine Complexes

  摘要：

  Cobalt complexes supported by diglyoxime ligands of the type Co(dmgBF(2))(2)(CH(3)CN)(2) and Co(dpgBF(2))(2)(CH(3)CN)(2) (where dmgBF(2) is difluoroboryl-dimethylglyoxime and dpgBF(2) is difluoroboryl-diphenylglyoxime), as well as cobalt complexes with [14]-tetraene-N(4) (Tim) ligands of the type [Co(Tim(R))X(2)](n+) (R = methyl or phenyl, X = Br or CH(3)CN; n = 1 with X = Br and n = 3 with X = CH(3)CN), have been observed to evolve H(2) electrocatalytically at potentials between -0.55 V and -0.20 V vs SCE in CH(3)CN. The complexes with more positive Co(II/I) redox potentials exhibited lower activity for H(2) production. For the complexes Co(dmgBF(2))(2)(CH(3)CN)(2), Co(dpgBF(2))(2)(CH(3)CN)(2), [Co(Tim(Me))Br(2)]Br, and [Co(Tim(Me))(CH(3)CN)(2)](BPh(4))(3), bulk electrolysis confirmed the catalytic nature of the process, with turnover numbers in excess of 5 and essentially quantitative faradaic yields for H(2) production. In contrast, the complexes [Co(Tim(Ph/Me))Br(2)]Br and [Co(Tim(Ph/Me))(CH(3)CN)(2)](BPh(4))(3) were less stable, and bulk electrolysis only produced faradaic yields for H(2) production of 20-25%. Cyclic voltammetry of Co(dmgBF(2))(2)(CH(3)CN)(2), [Co(Tim(Me))Br(2)](+), and [Co(Tim(Me))(CH(3)CN)(2)](3+) in the presence of acid revealed redox waves consistent with the Co(III)-H/Co(II)-H couple, suggesting the presence of Co(III) hydride intermediates in the catalytic system. The potentials at which these Co complexes catalyzed H(2) evolution were close to the reported thermodynamic potentials for the production of H(2) from protons in CH(3)CN, with the smallest overpotential being 40 mV for Co(dmgBF(2))(2)(CH(3)CN)(2) determined by electrochemistry. Consistent with this small overpotential, Co(dmgBF(2))(2)(CH(3)CN)(2) was also able to oxidize H(2) in the presence of a suitable conjugate base. Digital simulations of the electrochemical data were used to study the mechanism of H(2) evolution catalysis, and these studies are discussed.

  DOI：

  10.1021/ja067876b
• 作为产物：
  描述：

  (difluoroboryl)diphenylglyoximatocobalt(II) bis(acetonitrile) 在 sodium mercury amalgam 作用下， 以 acetonitrile 为溶剂， 生成 Na[(difluoroboryldiphenylglyoxime)2Co(acetonitrile)]
  参考文献：
  名称：

  析氢钴二乙肟催化剂的电子转移反应动力学

  摘要：

  Co-diglyoxime 配合物催化 H(2) 从质子解决方案在适度的超电势演化。还原为 Co(I) 后，通过与质子供体反应形成 Co(III)-氢化物。分析了 H(2) 生产的两种途径：一种是涉及氢化物质子化以释放 H(2) 并生成 Co(III) 的异裂途径；另一种是需要结合两个 Co(III)-氢化物的同型途径。速率常数和重组参数是根据激光快速淬火动力学实验的分析估算的（Co(III)-Co(II) 自交换 k = 9.5 x 10(-8) - 2.6 x 10(-5) M(-1) ) s(-1); lambda = 3.9 (+/-0.3) eV: Co(II)-Co(I) 自交换 k = 1.2 (+/-0.5) x 10(5) M(-1) s (-1)；λ = 1.4 (+/-0.05) eV)。

  DOI：

  10.1021/ja9080259