cobalt(I) 2,9,16,23-tetrasulfonatophthalocyanine(5-) | 86766-38-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cobalt(I) 2,9,16,23-tetrasulfonatophthalocyanine(5-)
• CAS: 86766-38-3
• 化学式: C₃₂H₁₂CoN₈O₁₂S₄
• 分子量: 887.751
• InChiKey: LVSBUGBGYCRBIQ-UHFFFAOYSA-J

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：

  cobalt(I) 2,9,16,23-tetrasulfonatophthalocyanine(5-) 在 氧气 作用下， 以 水 为溶剂， 以100%的产率得到cobalt(II) 2,9,16,23-tetrasulfonatophthalocyanine(4-) dimer
  参考文献：
  名称：

  Reduction of Cobalt and Iron Phthalocyanines and the Role of the Reduced Species in Catalyzed Photoreduction of CO₂

  摘要：

  The role of cobalt and iron phthalocyanines in catalytic CO2 reduction has been studied. Chemical, photochemical, and radiolytic reductions of the metal phthalocyanines (Pc) have been carried out in organic solvents, and reduction of their tetrasulfonated derivatives (TSPc) in aqueous solutions. (CoPc)-Pc-II and (FePc)-Pc-II are readily reduced to [(CoPc)-Pc-I](-) and [F-I'Pc](-), which do not react with CO2. Reduction of [(CoPc)-Pc-I](-) yields a product which is characterized as the radical anion, [(CoPc.-)-Pc-I](2-), on the basis of its absorption spectra in the visible and IR regions. This species is stable under dry anaerobic conditions and reacts rapidly with CO2. Catalytic formation of CO and formate is confirmed by photochemical experiments in DMF and acetonitrile solutions containing triethylamine (TEA) as a reductive quencher. The photochemical yields are greatly enhanced by the addition of p-terphenyl (TP). The radical anion, TP.-, formed from the reductive quenching of the singlet excited state with TEA, reduces the phthalocyanines very rapidly. The rate constants for reduction of (CoPc)-Pc-II, [(CoPc)-Pc-I](-), and [(FePc)-Pc-I](-) by TP.-, determined by pulse radiolysis in DMF solutions, are nearly diffusion-controlled. The mono-reduced species formed from [(CoPc)-Pc-I](-) is unstable under the pulse radiolysis conditions but is longer-lived under the flash photolysis conditions. The interaction of this species with CO2 is either too weak or too slow to detect in the current experiments, where a competing reaction with protons predominates.

  DOI：

  10.1021/jp002709y
• 作为产物：
  描述：

  cobalt(II) 2,9,16,23-tetrasulfonatophthalocyanine(4-) 在 氢气 、 钯 作用下， 以 水 、 异丙醇 为溶剂， 生成 cobalt(I) 2,9,16,23-tetrasulfonatophthalocyanine(5-)
  参考文献：
  名称：

  Reduction of Cobalt and Iron Phthalocyanines and the Role of the Reduced Species in Catalyzed Photoreduction of CO₂

  摘要：

  The role of cobalt and iron phthalocyanines in catalytic CO2 reduction has been studied. Chemical, photochemical, and radiolytic reductions of the metal phthalocyanines (Pc) have been carried out in organic solvents, and reduction of their tetrasulfonated derivatives (TSPc) in aqueous solutions. (CoPc)-Pc-II and (FePc)-Pc-II are readily reduced to [(CoPc)-Pc-I](-) and [F-I'Pc](-), which do not react with CO2. Reduction of [(CoPc)-Pc-I](-) yields a product which is characterized as the radical anion, [(CoPc.-)-Pc-I](2-), on the basis of its absorption spectra in the visible and IR regions. This species is stable under dry anaerobic conditions and reacts rapidly with CO2. Catalytic formation of CO and formate is confirmed by photochemical experiments in DMF and acetonitrile solutions containing triethylamine (TEA) as a reductive quencher. The photochemical yields are greatly enhanced by the addition of p-terphenyl (TP). The radical anion, TP.-, formed from the reductive quenching of the singlet excited state with TEA, reduces the phthalocyanines very rapidly. The rate constants for reduction of (CoPc)-Pc-II, [(CoPc)-Pc-I](-), and [(FePc)-Pc-I](-) by TP.-, determined by pulse radiolysis in DMF solutions, are nearly diffusion-controlled. The mono-reduced species formed from [(CoPc)-Pc-I](-) is unstable under the pulse radiolysis conditions but is longer-lived under the flash photolysis conditions. The interaction of this species with CO2 is either too weak or too slow to detect in the current experiments, where a competing reaction with protons predominates.

  DOI：

  10.1021/jp002709y

文献信息

• Free radical reactions with dimeric cobalt(II) sulphophthalocyanine. A pulse radiolytic study
  作者：Guillermo Ferraudi、Larry K. Patterson

  DOI：10.1039/dt9800000476

  日期：——

  Reactions of cobalt(II) sulphophthalocyanine dimers with the free radicals e–(aq), OH, ĊH2OH, Me2C(OH)ĊH2, and Me2ĊOH have been investigated by optical pulse-radiolysis methods. Rate constants have been determined to be ca. 3 × 109 dm3 mol–1 s–1 for OH and e–(aq), but an order of magnitude less for the alcohol radicals. Similarity has been observed in the spectra produced by OH and Me2C(OH)ĊH2 although

  钴的反应（II）与所述自由基sulphophthalocyanine二聚体ë - （水溶液），OH，CH 2 OH中，Me 2 C（OH）CH 2，和Me 2 COH已经由光学脉冲辐解方法调查。速率常数已确定为ca。OH和e –（aq）为3×10 9 dm 3 mol –1 s –1，但醇自由基的数量级要少一个数量级。相似性在由OH和Me产生的光谱中观察到2 C（OH）CH 2尽管动力学明显不同。提出在通过OH形成配体基团之后，金属中心的氧化和随后的二聚体分裂发生。在我的情况下2 C（OH）CH 2的金属-烷基键的形成出现的几率，其次是二聚中间的分裂。通过e所产生的瞬态光谱- （水溶液），CH 2 OH，和Me 2 COH也非常彼此相似。在这些情况下的光谱行为表明通过的配体基团，随后二聚体离解（还原金属中心的吨½约2毫秒）。