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化学学报
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化学学报 ›› 2001, Vol. 59 ›› Issue (1): 137-141. 上一篇    下一篇

研究论文

双卟啉双钴配合物与双氧作用的热力学及ESR研究

周晓海;卢卫兵;邓立志;朱银燕;任建国;张绍辉;汪存信   

  1. 武汉大学化学与环境科学学院;南京大学配位化学国家重点实验室.南京 (210008)
  • 发布日期:2001-01-15

Thermodynamic and ESR study on the reaction of dicobalt(Ⅱ) diporphyrin complex with dioxygen

Zhou Xiaohai;Lu Weibing;Deng Lizhi;Zhu Yinyan;Ren Jianguo;Zhang Shaohui;Wang Cunxin   

  1. Nanjing Univ, Coordinat Chem State Key Lab.Nanjing(210008)
  • Published:2001-01-15

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被引次数

2 | 1

用电子光谱法研究了一种由六个碳原子的脂肪二酰胺链连接两个四苯基卟啉的双核钴(Ⅱ)配合物(Co~2PP~4)在DMF溶液中与双氧的可逆结合作用，测定了反应的Hill系数n=1.84，△G^0(298K)=-12.3kJ·mol^-^1，P~1~/~2=6.8kPa，热力学数据表明Co~2PP~4分子内两个金属卟啉环之间存在着强的协同作用。由双卟啉双钴(Ⅱ)配合物与双氧作用形成的配合物经ESR证实为超氧金属配合物，结合方式属于Co-O~2^-超氧类型。

关键词: 卟啉, 钴络合物, 电子自旋共振, 电子光谱学, 酰胺P

The reaction of dioxygen with a dicobalt di(meso- tetraphenylporphyrin) linked by a diamido-aliphatic chain in N,N- dimethylformamide solution was studied. Thermodynamic values under standard state (298K, 100kPa O~2) are: P~1~/~2=6.8 kPa, =1.84, △G^0 (298K)=-12.3kJ·mol^-^1, △H^0=-172.09kJ·mol^-^1, △S^0=-536.21 J· mol^-^1·K^-^1. thermodynamic data show that each of the two cobalt(Ⅱ) porphyrin rings has strong cooperative effect of oxygen binding with another. The reaction of dioxygen with the complex was also studied by ESR spectroscopy. The results show that bonding way of dioxygen complex is of the superoxo Co-O~2^- type.

Key words: PORPHYRIN, COBALT COMPLEX, ELECTRON SPIN RESONANCE, ELECTRON SPECTROSCOPY, AMIDES P

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