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Éric Gouré

Amine transfer reactions catalyzed by binuclear non heme iron systems: High oxidation state intermediates

Published on 26 September 2008


Thesis presented September 26, 2008

Abstract:
With the aim of understanding mechanisms of metal-catalyzed amine transfer reactions, we have synthesized a diiron complex with an internal aromatic substrate. In presence of amine donor as ArINTs, this complex performs the quantitative intramolecular aromatic amination of a benzyl group of the ligand and this amination produces both mono and bis(tosylamine) derivatives. The amination mechanism fully characterized. We have been provide indirect evidences for both a FeIIIFeIV(=NTs) and a FeIVFeIV(=NTs)(NHTs) intermediate using isotop​e labelling experiments coupled with ESI-MS analysis and HPLC quantification of reaction products.
The second part of this work deals with a non heme mixed valence diiron complex with an aniline ligand. The reversible deprotonation of the aniline group leads to the formation of the corresponding anilinate complex and induces a valence inversion of the metal ions.

Keywords:
Diiron complexes, biomimetism, amine transfer, mechanistic studies, mass spectrometry, isotopic labelling, valence inversion, amine detector, intermediate

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