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Synthèse et étude de complexes di- et tri- nucléaires du fer inspirés du site actif des hydrogénases [FeFe]

Abstract : Hydrogenases are metalloenzymes found in Nature which are able to catalyse the production and the uptake of dihydrogen. Reports orr the structures of these hydrogénases have revealed the organometallic nature of their active sites, which are based on bimetallic assemblies containing nickel and iron atoms. Therefore, many diiron complexes have been synthesized in order to understand and to reproduce the high efficiency of [FeFe]- hydrogenases towards the reversible conversion of protons into dihydrogen. In particular, dithiolato-bridged diiron compounds, with bidentate ligands, have been developed in reason of results of theoretical studies which have suggested that an asymmetrical disubstitution at one iron atom of such bioinspired molecules may allow to reproduce some structural key features of the active site. One part of the works reported in this thesis concems pursuing studies previously undertaken in the laboratory on the use of bidentate chelating ligands with diiron bioinspired models of [FeFe] hydrogenases, such as 1,10- phenanthroline or diphosphines. Another part reports the development of a systematîc way for the synthesis of original trinuclear iron clusters having a quasi-linear arrangement of the three iron atoms. Electrochemical behaviours of the synthesized species as well as their reactivity in acidic medium have been studied.
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  • HAL Id : tel-02009518, version 1


Laëtitia Beaume. Synthèse et étude de complexes di- et tri- nucléaires du fer inspirés du site actif des hydrogénases [FeFe]. Autre. Université de Bretagne occidentale - Brest, 2015. Français. ⟨NNT : 2015BRES0010⟩. ⟨tel-02009518⟩



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