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Complexes pince et cooperativité métal/ligand : application en catalyse

Abstract : This Ph.D. work deals with organometallic chemistry of indenyl/indenediide palladium and platinum pincer complexes and their applications in metal-ligand cooperative catalysis. The first chapter of this manuscript compiled a non-exhaustive bibliographic survey of the field of metal-ligand cooperation, from Noyori's system applied to the asymmetric hydrogenation, to the recent examples described by Milstein involving non-aromatic pincer ligands. Pincer ligands are also presented. Starting from the first example, in which Shaw shed light a PCP pincer, to the contemporary CNC pincer reported by Bezuidenhout. The versatility of those ligands is illustrated through few modulations allowing originals reactivities or stabilisation of highly unstable species. The second chapter is focused on the development of a new catalytic reaction with the indenediide palladium pincer complex. This reaction entail, for the first time, two substrates, the CO2 as a C1 source and propargylamines/homopropargylamines. The mechanistic studies turn out the importance of the metal-ligand cooperativity. Then, the third chapter concerns exploratory chemistry. New reactivities have been studied with the platinum complexes. The activation of low polar bond such as H-H and H-Si allowed the reduction of unsatured C-C bond. The mechanistic propositions, that remain to be confirmed, seem to indicate the feasibility of ? bond metathesis and migratory insertions. Finally, the last chapter is dedicated to the development of a new ligand. The latter showed the distinctive characteristic to be hemilabile, leading the way of new reactivities. His coordination to palladium, followed by his deprotonation to give rise to the non-innocent nature of the complex is presented, as well as the application of the resulting complex in the context of a cycloisomerisation. Those results are reflecting the importance of the indenyl and indenediide pincer ligands besides the metal-ligand cooperativity in catalysis.
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Paul Brunel. Complexes pince et cooperativité métal/ligand : application en catalyse. Chimie de coordination. Université Paul Sabatier - Toulouse III, 2018. Français. ⟨NNT : 2018TOU30275⟩. ⟨tel-02338889⟩

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