Abstract
Compound I, an oxo–iron(IV) porphyrin π-cation radical species, and its one-electron-reduced form compound II are regarded as key intermediates in reactions catalyzed by cytochrome P450. Although both reactive intermediates can be easily produced from model systems such as iron(III) meso-tetra(2,4,6-trimethylphenyl)porphyrin hydroxide by selecting appropriate reaction conditions, there are only a few thermal activation parameters reported for the reactions of compound I analogues, whereas such parameters for the reactions of compound II analogues have not been investigated so far. Our study demonstrates that ΔH ≠ and ΔS ≠ are closely related to the chemical nature of the substrate and the reactive intermediate (viz., compounds I and II) in epoxidation and C–H abstraction reactions. Although most studied reactions appear to be enthalpy-controlled (i.e., ΔH ≠ > −TΔS ≠), different results were found for C–H abstractions catalyzed by compound I. Whereas the reaction with 9,10-dihydroanthracene as a substrate is also dominated by the activation enthalpy (ΔH ≠ = 42 kJ/mol, ΔS ≠ = 41 J/Kmol), the same reaction with xanthene shows a large contribution from the activation entropy (ΔH ≠ = 24 kJ/mol, ΔS ≠ = −100 J/kmol). This is of special interest since the activation barrier for entropy-controlled reactions shows a significant dependence on temperature, which can have an important impact on the relative reaction rates. As a consequence, a close correlation between bond strength and reaction rate—as commonly assumed for C–H abstraction reactions—no longer exists. In this way, this study can contribute to a proper evaluation of experimental and computational data, and to a deeper understanding of mechanistic aspects that account for differences in the reactivity of compounds I and II.
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The authors gratefully acknowledge continued financial support from the Deutsche Forschungsgemeinschaft.
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Fertinger, C., Franke, A. & van Eldik, R. Mechanistic insight from thermal activation parameters for oxygenation reactions of different substrates with biomimetic iron porphyrin models for compounds I and II. J Biol Inorg Chem 17, 27–36 (2012). https://doi.org/10.1007/s00775-011-0822-7
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DOI: https://doi.org/10.1007/s00775-011-0822-7