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Nouvelles paires de Lewis frustrées à partir de complexes du groupe 6 et de boranes pour l'activation du diazote et sa fonctionnalisation

Abstract : Molecular nitrogen activation and functionalization are among the most important challenge in modern chemistry, motivated by the need to freeing us from the use of the Haber-Bosch process. Indeed, this process used for the industrial synthesis of ammonia of which current agriculture depend and is strongly energy demanding. The goal of this Ph.D. work was the synthesis of new frustrated Lewis pair form different group 6 dinitrogen complexes and boranes to enable dinitrogen activation and its functionalization in mild conditions. The first part of this manuscript presents the synthesis of frustrated Lewis pairs between molybdenum and tungsten dinitrogen complexes and tris(pentafluorophenyl). Attempts of functionalization of dinitrogen inspired from the frustrated Lewis pair chemistry and leading to formation of N-B and N-Si bonds are described in this part. The oxidative addition of dihydrogen onto metallic centres, leading to heptacoordinated complexes, was substantially demonstrated for those original Lewis pairs. In the second chapter, the reaction of the same molybdenum and tungsten dinitrogen complexes with the Piers' borane enabled us to uncover the first 1,3-addition of the B-H bond on a M-N≡N unit. This result could be extended to other hydroboranes by the rational use of a catalytic amount of Piers' borane. Dihydrogen was also activated by a specific complex in this chapter. Finally, a molybdenum nitride complex was prepared in order to use it as a Lewis Base in a frustrated Lewis pair system. These experiments, discussed in the third chapter, led to the formation of two adducts that could be involved into reactions enabling the formation of N-B and N-Si bonds.
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Anaïs Coffinet. Nouvelles paires de Lewis frustrées à partir de complexes du groupe 6 et de boranes pour l'activation du diazote et sa fonctionnalisation. Chimie de coordination. Université Paul Sabatier - Toulouse III, 2020. Français. ⟨NNT : 2020TOU30125⟩. ⟨tel-03148892⟩

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