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<dc:title xml:lang="fr">Synthèse de complexes métalliques et leurs applications en polymérisation de polyesters, en catalyse et en photo-physique.</dc:title>
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<dc:subject xml:lang="fr">Chimie de coordination</dc:subject>
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<dc:subject xml:lang="fr">Polymérisation de polyesters</dc:subject>
<dc:subject xml:lang="fr">Déshydrogénation oxydante</dc:subject>
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<dc:subject xml:lang="en">Coordination chemistry</dc:subject>
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<dc:subject xml:lang="en">Catalysis</dc:subject>
<dc:subject xml:lang="en">Polyester polymerization</dc:subject>
<dc:subject xml:lang="en">Oxidative dehydrogenation</dc:subject>
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<dcterms:abstract xml:lang="fr">Dans un projet mené en étroite collaboration avec une industrie chimique, la problématique initiale a été de développer de nouveaux catalyseurs industriels de polycondensation à base de titane pour la production de polyéthylène téréphtalate. La valorisation du TiCl3OEt, un sous-produit industriel, a permis de développer une série de catalyseurs de polycondensation. Les résultats de polymérisation indiquent que la plupart de nos systèmes catalytiques sont aussi bons voir meilleurs que les catalyseurs commerciaux. Parallèlement, nous nous sommes intéressés à la synthèse de complexes de ruthénium(II) en vue de catalyser la réaction de double déshydrogénation oxydante d’amine primaire en nitrile. Dans un premier temps, nous avons remarqué que le complexe [Ru(p-cym)Cl2]2 était capable de convertir des amines primaires en nitriles, sans ajout supplémentaire de ligand ou d’additifs. Afin d’améliorer les rendements et la sélectivité, nous avons synthétisé plusieurs complexes originaux de ruthénium(II), stabilisés par un ligand bidendate NHC-thioether. Pour finir, afin de valoriser des phosphines produites au laboratoire, nous nous sommes intéressés à la préparation de complexes de cuivre(I). La synthèse, par méchanochimie, nous a permis d’obtenir rapidement les complexes dinucléaires correspondants avec de bons rendements. Les différents complexes exhibent tous une intense photoluminescence à l’état solide avec de bons rendements quantiques.</dcterms:abstract>
<dcterms:abstract xml:lang="en">In a project carried out in close collaboration with a chemical industry, the initial problem was to develop new titanium-based industrial polycondensation catalysts for the production of polyethylene terephthalate. The valorization of TiCl3OEt, an industrial by-product, allowed the development of a series of polycondensation catalysts. Polymerization results indicate that most of our catalyst systems are as good as or better than commercial catalysts. In parallel, we have been interested in the synthesis of ruthenium(II) complexes to catalyze the oxidative double dehydrogenation reaction of primary amine to nitrile. In a first step, we noticed that the [Ru(p-cym)Cl2]2 complex was capable of converting primary amines into nitriles, without the addition of additional ligand or additives. In order to improve yields and selectivity, we synthesized several original ruthenium(II) complexes stabilized by a bidendate NHC-thioether ligand. Finally, in order to enhance the value of phosphines produced in the laboratory, we were interested in the preparation of copper(I) complexes. The synthesis, by mechanochemistry, allowed us to quickly obtain the corresponding dinuclear complexes with good yields. The different complexes all exhibit intense solid-state photoluminescence with good quantum yields.</dcterms:abstract>
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