Frédéric Avenier
Mechanistic study of the reactions of oxygen and amine transfer catalyzed by dinuclear complexes of iron: Biomimetic and catalysis
Published on 30 October 2003
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Thesis presented October 30, 2003
Abstract:
With the aim of mimicking the activity of diiron hydroxylase enzymes, we have synthesized diiron model complexes with an internal substrate (aromatic or aliphatic) and made them react with various oxygen donors (mCPBA, ArIO, H2O2). We have first characterized the reaction products and then studied the oxygen transfer mechanism using isotope labelling experiments coupled with ESI-MS analysis. This allowed us to suggest different hydroxylation mechanisms depending on the oxygen donor used. We notably exhibit indirect evidence for a FeIV2O2 intermediate when hydroxylation is done with
mCPBA. The second part of this work deals with amine transfer instead of oxygen transfer, using ArINTs. We demonstrate that our system is very efficient for aromatic and aliphatic intra-molecular amidation, but it also catalyzes olefin aziridination, aliphatic amidation and sulfur sulfoxidation in good yields.
Keywords:
Diiron complexes, biomimetic activity, oxygen transfer, amine transfer, mechanistic studies, mass spectrometry, isotope labelling experiments, catalysis
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