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Catalyse coopérative avec les ligands rédox non-innocents : processus radicalaires et organométalliques

Abstract : Because of their ability to get involved in redox events, non-innocents ligands have long sparked the interest of spectroscopists, and their potential in catalysis has only later been considered. Iminosemiquinonate radical ligands and their derivatives are well-established non-innocent ligands and have been previously used with several metals, showing their efficiency in specific synthetic applications, such as oxidations and cross-couplings. This thesis work deals with the development of reactivities using iminosemiquinonate copper and nickel complexes. First, the ability of these complexes to induce the controlled generation of CF3 radicals by reduction of a CF3+ source was demonstrated, and key organometallic species resulting from a ligand-centered single electron transfer were identified using UV-vis spectroscopy. Catalytic conditions were developed and applied to the trifluoromethylation of silyl enol ethers, heteroarenes and hydrotrifluoromethylation of alkynes. Then, the synthesis of the first well-defined CuII–CF3 complex bearing fully oxidized iminobenzoquinone ligands was achieved. The study of its reactivity revealed the prominent role of the redox ligands, which stabilize a (+II) oxidation state without preventing its ability to behave as a high-valent CuIII complex. These observations were substantiated by a combination of advanced EPR spectroscopy techniques with DFT calculations. Finally, the influence of iminosemiquinonate ligands on the structure and the reactivity of copper–nitrene species, in catalytic nitrene transfer reactions, is the focus of a last project, which is still in progress.
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Submitted on : Friday, December 1, 2017 - 8:55:52 AM
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  • HAL Id : tel-01653080, version 1


Jérémy Jacquet. Catalyse coopérative avec les ligands rédox non-innocents : processus radicalaires et organométalliques. Chimie analytique. Université Pierre et Marie Curie - Paris VI, 2016. Français. ⟨NNT : 2016PA066398⟩. ⟨tel-01653080⟩



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