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Les iminophosphoranes : synthèse, propriétés en coordination et applications en catalyse.

Abstract : Iminophosphoranes, the nitrogen analogues of phosphorus ylides, are very strong donors able to coordinate hard metal centers. Although the Staudinger approach (azides) is the most utilized methodology to synthesize iminophosphoranes, it restricts the nature of substituent on the nitrogen atom. In particular, the highly desirable chiral versions are not easily accessible via this strategy. An easy and versatile methodology toward mixed heterofunctionnal ligands such as phosphine~iminophosphorane and phosphine~iminophosphorane~amine, was developed, based on the Kirsanov approach. Having in hands bidentate, tridentate and tetradentate ligands, the coordination towards several metal centers (Ni, Ru, Pd...) has been explored. In particular, ruthenium complexes were tested in catalytic transfer hydrogenation of ketones which allowed us to isolate and characterize by X-ray diffraction, a highly reactive hydridoamido species. Th! e donation ability of several bidentate ligands (N,N) and (P,N) has been investigated by electrochemical oxidation. The corresponding radical cations have been characterized on the one hand by cyclic voltammetry and EPR and on the other hand by DFT calculations. Finally, the Kirsanov methodology allowed us to isolate and characterize the first chiral dianion bis(iminophosphoranyl)methandiide. This dianion is a carbene precursor with promising applications both in coordination and enantioselective catalysis.
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Submitted on : Wednesday, July 28, 2010 - 3:17:56 PM
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Leila Boubekeur. Les iminophosphoranes : synthèse, propriétés en coordination et applications en catalyse.. Chimie de coordination. Ecole Polytechnique X, 2006. Français. ⟨pastel-00001980⟩

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