Thèse de doctorat en Sciences chimiques
Sous la direction de Marc Mauduit.
Soutenue en 2011
à Rennes, Ecole nationale supérieure de chimie , dans le cadre de École doctorale Sciences de la matière (Rennes) , en partenariat avec Institut des Sciences Chimiques de Rennes (laboratoire) et de Université européenne de Bretagne (autre partenaire) .
Modification of ruthenium complexes : towards a better control of the catalyst properties for olefin metathesis
This work deals with the synthesis of new ruthenium-based complexes for olefin metathesis. In a first part, the development of new homogeneous ruthenium catalyst has been done. The introduction of new Nheterocyclic carbènes, styrenylether ligands or pyridine-carboxylates gave new catalysts showing new activity and chemical stability properties. Indeed, latent catalysts, requiring an external activation or catalyst showing a very fast initiation rate have been synthesized and studied in several metathesis transformations. In a second part, new supported catalysts have been developed to improve the recycling of the ruthenium complex and facilitate the removal of ruthenium wastes in the final products. A new generation of ionic tagged catalyst has been synthesized enabling to increase the catalyst activity even at low catalyst loading (< 1 mol%). Then, a new concept for supporting ruthenium complexes have been developed. The use of charge transfert complexe (CTC) tag, allowing an easier anchorage of the catalyst on silica support, showed promising results to decrease the ruthenium contamination in the final product.