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O_2反应  

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

作　　者：王清民[1] 杨国昱[1] 于连香[1] 宋扬[1] 孙晋峰[1] 曹锡章 

机构地区：[1]吉林大学化学系

出　　处：《高等学校化学学报》1994年第10期1429-1432,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金;国家重点实验室资助

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Ｏ_２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Ｏ_２反应的速率越大。In various organic solvents,the photochemical behavior of Co(Ⅱ)TPP has been investigated.The experiment results suggested that in polar solvent the photooxidation reac tion of Co(Ⅱ)TPP took 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)TPP also 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)TPP promoted 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)TPP is 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.

关 键 词：四苯基钴卟啉 光助还原 氧气 

分 类 号：O644.13[理学—物理化学]