Phosphabarrélènes et Carbènes en Catalyse ; De l'Influence du Ligand à la Conception de Nouveaux Systèmes Bidentes ; Etude Expérimentale et Théorique

Abstract : Phosphabarrelenes are unique ligands among phosphines: they combine a very rare set of properties as they are at once sterically hindered and electronically acceptor. The first part of this work deals with the consequences in several palladium catalytic processes involved by these properties. Every single step of the catalytic cycles is thus analyzed both by experimental and theoretical approaches and observations are considered with references to the ligand properties. Some advantages of using phosphabarrelenes are found especially for the two elementary steps of transmetallation and reductive elimination. Conclusions are finally given thanks to the two angles of computational calculation and experimentation. In a second time, the study goes on with nickel. Even though its association with phosphabarrelenes looks promising, these complexes turn out to be poorly efficient compared to already reported examples. The study is thus refocused on carbenes, another familly of ligands. These two first parts exhibit the interest that bidental phosphabarrelenes could have. The synthesis of such molecules is the main objective of the final part. In particular, mechanisms leading to these functionalized phosphines starting with the corresponding phosphinines are investigated, either by nucleophilic addition or Diels-Alder reaction.
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Philippe Ribagnac. Phosphabarrélènes et Carbènes en Catalyse ; De l'Influence du Ligand à la Conception de Nouveaux Systèmes Bidentes ; Etude Expérimentale et Théorique. Catalyse. Ecole Polytechnique X, 2012. Français. ⟨pastel-00819440⟩

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