Les dianions géminés comme précurseurs pour la synthèse de complexes carbéniques de métaux de transition

Abstract : Recently, a new method for the synthesis of carbene complexes of transition metal has been developed. The strategy consists in bringing the four electrons of the metal-carbon double bond by the carbene fragment. In this respect the use of geminal dianions, species in which the central carbon bears two lone pairs, incorporating σ4-P groups has been a major breakthrough. The use of these dianions has allowed the synthesis of many carbene complexes of transition metal, rare earths, lanthanides and actinides. The first aim of this doctoral work was to extend the coordination study of known dianions. Thus, new carbene complexes have been synthesized. These complexes have been studied theoretically in order to clarify the nature of the metal-carbon bond. Then, we have shown that carbene complexes of group 4 metal centers synthesized by our method could act as stoichiometric transfer agents of the carbene moiety. This method allows the synthesis of new complexes unavailable by the dianion route. The second aim of this work was to extend the number of accessible dianions. The stability of such species highly depends on the choice of the substituents at the phosphorous atoms and the synthesis of such species requires accurate experimental procedures. Three new dianions have been synthesized and characterized. The stabilization of the lone pair at the central carbon has been studied in each case. The first results on the coordination chemistry of these species are also presented. Finally, the activation of B-H bonds by carbenoid species obtained by oxidation of our dianions is reported.
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Submitted on : Wednesday, December 5, 2012 - 10:55:44 AM
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Hadrien Heuclin. Les dianions géminés comme précurseurs pour la synthèse de complexes carbéniques de métaux de transition. Chimie de coordination. Ecole Polytechnique X, 2012. Français. ⟨pastel-00761254⟩

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