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Chimie de coordination du baryum : synthèse et applications en catalyse

Abstract : Heavy alkaline earth metals chemistry (calcium, strontium and barium) has been described as difficult and unpredictable for a long time, unlike the chemistry of magnesium, their lightest congener. However, in the last decades, many complexes based heavy alkaline earth metals have emerged as effective precatalysts for many applications and organic transformations (polymerization, hydroelementation, dehydrogenating coupling, etc.). This thesis describes the synthesis and study (experimental and theoretical) of new low-coordinate barium complexes based on electron-poor alkoxide ligands. The study of these compounds has improved our understanding of the different phenomena required to stabilize such compounds. Then, two new dehydrocoupling systems BO-H/H-Si and SiO-H/H-Si were developed and studied. These systems have allowed the catalytic formation of borasiloxanes and asymmetric siloxanes in a selective manner. Finally, this work shows the synthesis and use of new ancillary ligands for the formation of stable heteroleptic barium complexes. The latter have demonstrated strong catalytic activity in hydrophosphination with TOFs up to 200 h-1 for the intermolecular hydrophosphination of styrene by HPPh2.
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Submitted on : Monday, January 27, 2020 - 9:42:09 AM
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Erwann Le Coz. Chimie de coordination du baryum : synthèse et applications en catalyse. Chimie de coordination. Université Rennes 1, 2019. Français. ⟨NNT : 2019REN1S052⟩. ⟨tel-02456011⟩



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