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Réactivité électrochimique de la porphine de magnésium : fonctionnalisation, oligo-polymérisation et application à la synthèse de porphyrines et multi-porphyrines

Abstract : This work deals with the redox reactivity of magnesium porphine, the study of its electropolymerization and resulting materials, of its functionalization by nucleophiles as well as the mechanistic investigation of the C-C oxidative coupling on a tris-meso-substituted porphyrin model.The electrochemical oxidation of magnesium porphine to its cation radical leads to oligomers in solution and polymers on the electrode, which molecular structure depends on the imposed potential. The reactivity of the cation radical has also been exploited by adding sufficient amount of nucleophiles (pyridine and triphenylphosphine) in the reactional in order to inhibit the oligomerization/polymerization process and to lead exclusively to the mono-substitution product. In spite of the two types of free positions on the porphyrin ring (meso and ? positions), the reaction is ideally regio-selective on the meso position. The analysis of a model derivative, a tris-meso-substituted porphyrin, thus having only one reactive site méso, rendered the mechanistic study of the C-C oxidative coupling easier since this one can only lead to the formation of the meso-meso dimer. In addition, the latter was electrosynthesized with high and competitive yields compared with those reported for the chemical way. Lastly, the anodic nucleophilic substitution (phosphination, nitration and pyridination) in meso position was extended to tris-meso-substituted porphyrins of nickel, magnesium and zinc. The nitro-porphyrin magnesium complex was converted quantitatively into amine by electrocatalytic hydrogenation
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Abdou Khadre Djily Dime. Réactivité électrochimique de la porphine de magnésium : fonctionnalisation, oligo-polymérisation et application à la synthèse de porphyrines et multi-porphyrines. Autre. Université de Bourgogne, 2012. Français. ⟨NNT : 2012DIJOS048⟩. ⟨tel-00909526⟩

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