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Synthèse et applications de complexes de nickel(II) pour l’optimisation et la compréhension des réactions d’hydrofonctionnalisation et d’activation C–H.

Abstract : The first study showed that among several half sandwich nickel complexes, [NiCp*Cl(IMes)] was the most active pre-catalyst for the hydroboration of styrene derivatives but also that the nature of the borane had a great influence on the addition regioselectivity. With optimized conditions in hand, we examined the scope of the reaction with HBPin and HBCat. In addition, mechanistic studies and isolation of a Ni(I) specie allowed us to propose a mechanism that takes all the previous results into account. The second study highlighted the good performances of (2-C,S)-[NiCp{Bn-NHC-(CH2)2-StBu}](PF6) for the hydrosilylation of aldehydes and ketones, confirming the concept of hemilability. This study has also been completed by the synthesis and the evaluation of the performance for the same reaction of (2-C,N)-[NiCp{Mes-NHC-CH2-Py}](Br) bearing a picolyl group that is apparently more coordinant than a sulfur group. Finally, the last study has been oriented toward the cyclonickelation of the dmba and the 2-phenylpyridine by means of AMLA/CMD mechanism already known with palladium.
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Franck Ulm. Synthèse et applications de complexes de nickel(II) pour l’optimisation et la compréhension des réactions d’hydrofonctionnalisation et d’activation C–H.. Chimie théorique et/ou physique. Université de Strasbourg, 2019. Français. ⟨NNT : 2019STRAF043⟩. ⟨tel-02992054⟩

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