高等学校化学学报 ›› 1994, Vol. 15 ›› Issue (10): 1429-1432.

• 论文 • 上一篇    下一篇

金属卟啉化合物光催化反应研究(Ⅳ)─四苯基钴卟啉光助还原O2反应

王清民, 杨国昱, 于连香, 宋扬, 孙晋峰, 曹锡章   

  1. 吉林大学化学系, 长春, 130023
  • 收稿日期:1993-10-13 修回日期:1994-06-10 出版日期:1994-10-24 发布日期:1994-10-24
  • 通讯作者: 杨国显.
  • 作者简介:王清民,男,32岁,硕士,讲师.
  • 基金资助:

    国家自然科学基金;国家重点实验室资助

Studies on the Photochemical Reactions Catalyzed by Metalloporphyrin Complexes(Ⅳ)─Kinetics of Photoassisted Reduction of Oxygen by Cobalt(Ⅱ)tetrakisphenylporphyrin

WANG Qing-Min, YANG Guo-Yu, YU Lian-Xiang, SONG Yang, SUN Jin-Feng, CAO Xi-Zhang   

  1. Department of Chemistry, Jilin University, Changchun, 130023
  • Received:1993-10-13 Revised:1994-06-10 Online:1994-10-24 Published:1994-10-24

摘要: 研究了不同的有机溶剂中四苯基钴卟啉(Co(Ⅱ)TPP)的光助还原O2反应,详细讨论了溶剂效应和有机碱的轴向配位效应对光还原反应的影响,同时对反应机理进行了探讨。结果表明,溶剂的极性越大或有机碱的轴向配位能力越强时,光还原O2反应的速率越大。

关键词: 光助还原, 溶剂效应, 轴向配位

Abstract: In various organic solvents, the photochemical behavior of Co(Ⅱ)TPPhas been investigated.The experiment results suggested that in polar solvent the photooxidation reac tion of Co(Ⅱ)TPPtook place, while it did not take place in non-polar and halogenated sol vents. In polar solvent, the organic bases could increase the photooxidation reaction rate of Co(Ⅱ)TPP, but in non-polar and hologenated solvents, the reaction of Co(Ⅱ)TPPalso took place when the organic base existed.This was bacause that the adducts formed by an axially coordinated polar solvent or organic bases and Co(Ⅱ)TPPpromoted greatly forming complex between oxygen and Co(Ⅱ)TPP(L).The electron complete transfer reaction be tween oxygen and Co(Ⅱ)center was accelerated greatly when the light irradiated.The ex perimental results indicate that when Co(Ⅱ)TPPis coordinated by polar solvents or organic bases in the fifth coordination position, the sixth position was greatly activated, which is the premise and key that superoxide complex formed between oxygen and Co(Ⅱ)TPP.

Key words: Photoassisted reduction, Solvent effect, Axially coordination