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Etudes autour de ligands phosphorés à grand angle de morsure à base de phospholes

Abstract : This thesis deals with the synthesis, characterisation and catalytic applications of phosphole- containing ligands having wide bite angles. The first section treats the chemistry of a rigid ligand (XDPP), which has phosphole substituents and a xanth-4,5-diyl backbone. After using XDPP to allow the synthesis and first X-ray characterisation of a gold hydride complex containing phosphine ligands, a mechanism for how these complexes catalyse the dehydrogenative silylation of alcohols is proposed on the basis of a combined experimental and computational study. Finally, a study of the deprotonation of XDPP is given. The second describes the diastereoselective synthesis of [16]-calix-[1]phosphaferrocene-[2]phosphole-[1]heterocycles, a series of flexible porphyrinoid heteromacrocycles containing phosphole units. Preliminary electrochemical measurements show interesting redox activity which results from reversible localisation of at least two electrons upon the macrocycle periphery. Coordination chemistry studies have allowed both kinetically and thermodynamically favoured complexes to be prepared; initial studies of Ag and Pd complexes showing intracavity coordination indicate that the ligand has a very large bite angle. In the final section, the concept of the "pseudodesymmetrisation" of dissymmetrically 2,5- diester- substituted phosphametallocenes is presented. Homologation strategies for the products, which could form the basis of a future route to enantiopure macrocycles, are given. The pseudodesymmetrisation methodology has also been used to allow the enantioconvergent synthesis of a modular class of phosphametallocene-phosphines to be achieved.
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Submitted on : Tuesday, January 29, 2013 - 11:23:01 AM
Last modification on : Wednesday, December 15, 2021 - 10:00:37 AM
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  • HAL Id : pastel-00782147, version 1



Aurelie Escalle-Lewis. Etudes autour de ligands phosphorés à grand angle de morsure à base de phospholes. Chimie de coordination. Ecole Polytechnique X, 2012. Français. ⟨pastel-00782147⟩



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