物理化学学报 >> 1995, Vol. 11 >> Issue (12): 1093-1096.doi: 10.3866/PKU.WHXB19951207

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咪唑钴(III)配合物还原动力学机理研究

章慧,颜文斌,周朝晖,徐志固   

  1. 厦门大学化学系，厦门 361005
  • 收稿日期:1994-09-19 修回日期:1995-02-25 发布日期:1995-12-15
  • 通讯作者: 周朝晖

Kinetic Investigation on the Mechanism of the Reduction of Imidazole Cobalt(III) Complexes

Zhang Hui,Yan Wen-Bin,Zhou Zhao-Hui,Xu Zhi-Gu   

  1. Department of Chemistry,Xiamen University,Xiamen 361005
  • Received:1994-09-19 Revised:1995-02-25 Published:1995-12-15
  • Contact: Zhou Zhao-Hui

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关键词: 电子转移反应, 外配位界机理, 咪唑配合物物, Co(III)配合物

Abstract:

Kinetic studies on the electron transfer(ET) reaction of [Co(NH3)5(ImH)]3+/[Fe(CN)6]4- and trans-[Co(NH3)(en)2(ImH)]3+/[Fe(CN)6]4- have been carried out at various temperatures. The results indicated that these two ET reactions followed the outer sphere mechanism. At 25℃,I=0.50mol L-1, the ion pair formation constants Qip of the precursor complexes in the ET reactions are 2.6×102 and 4.9 × 102mol L-1 ,and the electron transfer rate constants kct are 2.1 ×10-4 and 5.2 ×10-5s-1 respectively. The activation enthalpy △Het≠ and the activation entropy △Set≠ of these two processes are 1.2×102, 0.8×102kJ/mol and 5.1×102, 3.6×102kJ/mol﹒K-1 respectively.

Key words: Electron transfer reaction, Outer sphere mechanism, Imidazole complex, Co(III) complex