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

Chem. J. Chinese Universities ›› 1994, Vol. 15 ›› Issue (10): 1429.

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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

Department of Chemistry, Jilin University, Changchun, 130023

Received:1993-10-13 Revised:1994-06-10 Online:1994-10-24 Published:1994-10-24

Abstract

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

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WANG Qing-Min, YANG Guo-Yu, YU Lian-Xiang, SONG Yang, SUN Jin-Feng, CAO Xi-Zhang. Studies on the Photochemical Reactions Catalyzed by Metalloporphyrin Complexes(Ⅳ)─Kinetics of Photoassisted Reduction of Oxygen by Cobalt(Ⅱ)tetrakisphenylporphyrin[J]. Chem. J. Chinese Universities, 1994, 15(10): 1429.

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

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