Ligands « Porphyrine-Carbène N-Hétérocyclique » Réglables et Réactifs à des Stimuli Externes pour la Catalyse – PORPH-NHC
Research into catalysis is a major field in applied science and involves many areas of chemistry, notably organometallic chemistry. The efficiency of transition metal complexes as catalysts is essentially governed by the choice of the complexing ligand. In this rapidly growing area, extensive efforts have been focused on stimuli-responsive ligands able to switch the reactivity of the catalyst between multiple states by external factors without extra-synthetic steps. Over the past twenty years, the N-heterocyclic carbenes (NHCs) has been the field of vivid scientific competition, and yielded successes in key areas of homogeneous catalysis. Thus, the incorporation of stimuli-responsive groups linked to N-heterocyclic carbene ligands would be of wide interest to tune the catalytic activity of the catalyst. For this project, we propose the use of porphyrins as tunable stimuli-responsive organic groups linked to the NHC ligand. The synthesis of NHC-metal complexes fused to the aromatic core of the porphyrin will be realized. The properties of the porphyrin-NHC metal complexes will be extensively studied in connexion with their electronic and catalytic properties. Two different ways will be used to modulate the electronic properties of the NHC-bound external metal centers, and thus their catalytic properties. This modulation can be realized (1) through the structural modifications brought to the porphyrin, i.e. variation of the inner metal and variation of the nature of the four meso aryl groups, or (2) by applying external-stimuli such as redox processes and light irradiation.
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