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Etude de complexes pour les réactions par transfert d’atome d’oxygène ou d’azote : de la synthèse à la photoactivation

Abstract : Processes of oxidation and amination hold an important place on an industrial level but the current available methods are polluting and non-sustainable. To perform these transformations in the contour of green catalysis, bio-inspired oxygen atom transfer (OAT) and nitrogen atom transfer (NAT) reactions were addressed. In the case of OAT, the mechanism for the formation of the active species, the highly oxidized metal-oxo, is rather well described, and the challenge relies in the design of ligands to stabilize such species. For NAT, this step is less studied which limits the development of new catalysts. An even more challenging task resides in the use of light energy to generate these active species in the perspective to replace the classic oxidants.During this thesis, two projects have been undertaken. Firstly, the synthesis of dipyrrin based ligands and the corresponding ruthenium complex was evaluated for their ability to perform OAT reactions using conventional oxidants or the electrochemical way. Regarding the NAT reactions, we have investigated on the electrochemical, chemical and photochemical activation of the known catalyst Rh2(esp)2. Our strategy consisted in the activation of the nitrogen atom donor substrate, the sulfonamidate, in the coordination sphere of the catalyst. We disclose the spectroscopic signatures for the stepwise activation of the catalyst-substrate form. This work has as objective to set us on the path to develop a sustainable way to perform these reactions.
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Submitted on : Saturday, April 14, 2018 - 1:01:16 AM
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Clémence Ducloiset. Etude de complexes pour les réactions par transfert d’atome d’oxygène ou d’azote : de la synthèse à la photoactivation. Chimie inorganique. Université Paris-Saclay, 2017. Français. ⟨NNT : 2017SACLS252⟩. ⟨tel-01766744⟩



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