[Co(o-iminothiobenzosemiquinone)] | 452080-61-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: [Co(o-iminothiobenzosemiquinone)]
• 英文别名: nickel bis(2-aminobenzenethiolate)；trans-Ni(2-aminobenzenethiolate)₂；trans-Ni(abt)₂；bis(2-amidothiophenolato)nickel(IV)；Ni(II)(o-NHC6H4S)2
• CAS: 452080-61-4；20003-99-0
• 化学式: C₁₂H₁₀N₂NiS₂
• 分子量: 305.047
• InChiKey: DCJANXOBYNTYLY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.24
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  24.06
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  [Co(o-iminothiobenzosemiquinone)] 在 bis(pentamethylcyclopentadienyl)cobalt(II) 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 [Ni(2-aminothiophenolate)2]
  参考文献：
  名称：

  Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water

  摘要：

  A series of nickel bis(chelate) complexes having square planar coordination are studied for light-driven and electrocatalytic hydrogen production from water. The complexes Ni(abt)2 (abt = 2-aminobenzenethiolate), Ni(mp)(2) (mp = 2-mercaptophenolate) and Ni(mpo)(2) (mpo = 2-mercaptopyridyl-N-oxide) are found to be active catalysts under light-driven conditions, using fluorescein (Fl) as the photosensitizer (PS) and triethanolamine (TEOA) as the sacrificial electron donor in water under basic pH (pH = 9.8). These molecular systems achieve a turnover number (TON) of similar to 6000 (relative to catalyst) and are stable for more than 100 h under H-2-generating conditions. When water-soluble CdSe quantum dots with tripodal S-donor capping agents are employed as PS and ascorbic acid (AA) is used as the sacrificial electron donor at pH 4.5, an active and robust system is obtained for the light-driven generation of H-2 from aqueous protons. A TON of over 280 000 is achieved for the three active catalysts. These complexes are also examined electrochemically in organic solvents with weak organic acids as the proton source and in aqueous and aqueous/organic media for proton reduction. The most active photochemical catalysts also show excellent electrocatalytic activity in neutral pH water, achieving Faradaic yields close to 100% under anaerobic conditions and similar to 80% under aerobic conditions.

  DOI：

  10.1021/acscatal.5b00045
• 作为产物：
  描述：

  [Ni(2-aminothiophenolate)2] 以 N,N-二甲基甲酰胺 为溶剂， 生成 [Co(o-iminothiobenzosemiquinone)]
  参考文献：
  名称：

  邻氨基苯硫醇过渡金属配合物的非线性光学研究

  摘要：

  三阶非线性极化，χ （3）XXXX的Co（III）和Ni（II）的配合物的溶液，ö -aminobenzenethiol，ö -NH 2 ç 6 ħ 4 SH，通过简并四波混频测量在0.164微米。在溶液中，发现Ni（o -NH 2 C 6 H 4 S）2的去质子化在空气存在下发生，并且通过温和的升温而加速，产生Ni（o -NHC 6 H 4 S）2。该复合物的〈λxxxx〉 = 2×10 −31大esu的估计χ （3）xxxx约为2×10 -9 esu。镍配合物的低能量ddd跃迁在1.1μm处测量，可能是其增强的三阶光学非线性的原因。

  DOI：

  10.1016/0009-2614(91)90295-k
• 作为试剂：
  描述：

  水 在 三乙醇胺 、 [Co(o-iminothiobenzosemiquinone)] 作用下， 以 水 为溶剂， 生成 氢气
  参考文献：
  名称：

  Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water

  摘要：

  A series of nickel bis(chelate) complexes having square planar coordination are studied for light-driven and electrocatalytic hydrogen production from water. The complexes Ni(abt)2 (abt = 2-aminobenzenethiolate), Ni(mp)(2) (mp = 2-mercaptophenolate) and Ni(mpo)(2) (mpo = 2-mercaptopyridyl-N-oxide) are found to be active catalysts under light-driven conditions, using fluorescein (Fl) as the photosensitizer (PS) and triethanolamine (TEOA) as the sacrificial electron donor in water under basic pH (pH = 9.8). These molecular systems achieve a turnover number (TON) of similar to 6000 (relative to catalyst) and are stable for more than 100 h under H-2-generating conditions. When water-soluble CdSe quantum dots with tripodal S-donor capping agents are employed as PS and ascorbic acid (AA) is used as the sacrificial electron donor at pH 4.5, an active and robust system is obtained for the light-driven generation of H-2 from aqueous protons. A TON of over 280 000 is achieved for the three active catalysts. These complexes are also examined electrochemically in organic solvents with weak organic acids as the proton source and in aqueous and aqueous/organic media for proton reduction. The most active photochemical catalysts also show excellent electrocatalytic activity in neutral pH water, achieving Faradaic yields close to 100% under anaerobic conditions and similar to 80% under aerobic conditions.

  DOI：

  10.1021/acscatal.5b00045

文献信息

• Strong Proton‐Electron Coupling in π‐Planar Metal Complex with Redox‐Active Ligands
  作者：Pingping Huang、Yukihiro Yoshida、Yoshiaki Nakano、Hideki Yamochi、Mikihiro Hayashi、Hiroshi Kitagawa

  DOI：10.1002/anie.202204521

  日期：2022.6.27

  The strong proton-electron coupling behavior of a π-planar nickel(II) complex with redox-active N,S-ligands was demonstrated using optical and electrochemical methods as well as theoretical calculations. The potential-pH diagram shows a significant shift in the acidity-dependent redox potential, which is supported by the calculated energetic stabilization of frontier orbitals by protonation.

  使用光学和电化学方法以及理论计算证明了具有氧化还原活性 N,S-配体的 π 平面镍 (II) 配合物的强质子 - 电子耦合行为。电位-pH 图显示了酸度依赖性氧化还原电位的显着变化，这得到了通过质子化计算的边界轨道的能量稳定性的支持。
• Nickel(IV)-Komplexe und ihre Bedeutung bei der Bildung des Carbonyls
  作者：W. Hieber、R. Br�ck

  DOI：10.1007/bf00590333

  日期：——
• Hieber, W.; Brueck, R., Zeitschrift fur Anorganische und Allgemeine Chemie
  作者：Hieber, W.、Brueck, R.

  DOI：——

  日期：——
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Ni: MVol.C2, 8.12, page 947 - 963
  作者：

  DOI：——

  日期：——
• Beloglazkina, E. K.; Moiseeva, A. A.; Churakov, A. V., Russian Chemical Bulletin, 2002, vol. 51, p. 467 - 475
  作者：Beloglazkina, E. K.、Moiseeva, A. A.、Churakov, A. V.、Orlov, I. S.、Zyk, N. V.、et al.

  DOI：——

  日期：——