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Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations

Zhengzheng Pan and Martin Newcomb

Inorg Chem Commun 14(6):3 (2011) PMID 21572532

Disproportionation of oxoiron(IV) porphyrin (Compound II) to oxoiron(IV) porphyrin radical cation (Compound I) was studied in three P450 model systems with different electronic structures. Direct conversion of Compound II to Compound I has been observed for 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP) in acid-catalyzed reactions in a mixed solvent of acetonitrile and water (1:1, v/v) containing excess m-CPBA oxidant, with a second-order rate constant of (1.3+/-0.2)x10^2M^-^1s^-^1. The acid-catalyzed disproportionation heavily depends on the electron demand of the substituted aryl groups on the porphyrin macrocycle. The disproportionation equilibrium constants show drastic change for the three porphyrin systems.

Copyright © 2011 Elsevier Ltd. All rights reserved.

DOI: 10.1016/j.inoche.2011.03.044
Version: za2963e q8za6 q8zb7 q8zc2 q8zd3 q8ze8 q8zfb q8zg6
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