Conformation Equilibrium of Iron(Ⅲ)-metal-free Porphyrin Dimers and Its Effect on Catalytic Activity for Cyclohexane Hydroxylation

Abstract

Abstract: A series of iron(Ⅲ)-metal-free porphyrin dimers covalently linked with -O(CH₂)_n O- chain( n =2～5) have been synthesized and characterized. By using UV-Visible spectra, an equilibrium of two different conformations of porphyrin dimers, open and closed, in chloroform solution has been observed for the first time. The intensity of adsorption band 680 nm may be related to the conformation equilibrium, the longer the length of the alkoxy chain, the stronger the intensity of band 680 nm is present. As a new model catalytic system of cytochrome P450, all these dimers have higher catalytic activities than the corresponding mono iron(Ⅲ) porphyrin, and their catalytic activities increase gradually with the increase of the length of flexible chain. The higher catalytic activities may be related to the steric hindrance and intramolecular electron transfer of the porphyrin dimers caused by the conformation equilibrium.

Key words: Iron(Ⅲ)-metal-free porphyrin dimer, Conformation equilibrium, Catalytic activity, Cyclohexane hydroxylation

CLC Number:

O614.33

TrendMD:

REN Qi-Zhi, HUANG Jin-Wang, LIU Zhan-Liang, JI Liang-Nian  . Conformation Equilibrium of Iron(Ⅲ)-metal-free Porphyrin Dimers and Its Effect on Catalytic Activity for Cyclohexane Hydroxylation[J]. Chem. J. Chinese Universities, 1998, 19(4): 497.

References

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