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Préparation de précurseurs de carbènes N-hétérocycliques bidentes, étude de leur complexation et catalyse

Abstract : Advances in the search of highly efficient complexes for catalysis have led to an intensive use of N-heterocyclic carbenes (NHCs). In the last fifteen years, this kind of ligands has gained a lot of attention, in comparison to others, by their ability to give access to highly stable and highly active complexes.
Recent studies on the synthesis of bidentates ligands bearing one NHC unit and a coordinating nitrogen, and their highly active complexes, have oriented us on the preparation of the similar ligands with others heteroatoms.

As part of this newly developed theme in our group, we have prepared two original synthetic pathways leading to new N-heterocyclic carbene precursors, composed of an imidazolium group and another coordinating group which will be a phosphine or a thioether.

The study of these ligands has enabled the development of a rich coordination chemistry with Ni, Pd, Rh, Ru and Ir. Four coordination modes have been shown: the coordination with only the heteroatom or the NHC, or a coordination of both the heteraoatom and NHC via a “normal” mode or an “abnormal” mode. Our studies have shown that the coordination mode adopted by the ligands
was correlated to the experimental conditions, the metal reactivity and its affinity for the heteroatom.

The preparation of such complexes allowed us to carry out some preliminary tests in hydrosilylation and hydrogenation with rhodium(I) complexes. A thorough study of the coupling reaction of a Grignard reagent with an aryl halide (Kumada-Corriu-Tamao reaction) was
undertaken with the nickel(II) complexes.
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Contributor : Joffrey Wolf <>
Submitted on : Tuesday, August 28, 2007 - 11:11:27 AM
Last modification on : Friday, March 12, 2021 - 1:32:04 PM
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  • HAL Id : tel-00168421, version 1



Joffrey Wolf. Préparation de précurseurs de carbènes N-hétérocycliques bidentes, étude de leur complexation et catalyse. Autre. Université Paul Sabatier - Toulouse III, 2007. Français. ⟨tel-00168421⟩



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