Public Thesis defense - IMCN

Design, synthesis and applications of phosphines and amines embedded triptycenes: exploring new reactivities in main-group and organometallic chemistry by Lei HU

Pour l’obtention du grade de Docteur en sciences

This PhD work was focused on the development of sterically hindered Lewis bases, in particular triaryl phosphines and amines, which then were employed for the rational design of frustrated Lewis pair catalysts. In this context, we prepared new types of FLPs by combining strong boron Lewis acids with the group XV (N, P) derived 9-hetero-triptycene. Initially, several novel synthetic approaches enabling the access to the 9-azatriptycene framework were attempted. We then turned our attention to the preparation of sterically hindered 9-phosphatriptycene scaffold. Two methodologies were developed allowing to reach unprecedented otho-substituted unsymmetrical 9-phosphatriptycene derivatives which include the first example of P-chirogenic 9-phosphatriptycene ever reported. By means of computational and experimental methods, the unique electronic and steric properties, and Brønsted and Lewis basicities of 9-phosphatriptycenes were quantified. The coordination of 9-phosphatriptycenes with transition metal (RhIII and AuI) was finally investigated and the resulting complexes were studied and characterized by IR, NMR, and X-ray diffraction crystallography. Lastly, the association of phosphatriptycenes with B(C6F5)3 was experimentally tested and applied as FLP catalyst, enabling the transition-metal-free hydrogenation reaction of unactivated alkenes under mild reaction condition.

Jury members :

• Prof. Raphaël Robiette (UCLouvain), supervisor
• Prof. Guillaume Berionni (Namur Institute of Structured Matter (Unamur), Belgium), supervisor
• Prof. Jean-François Gohy (UCLouvain), chairperson
• Prof. Michael Singleton (UCLouvain), secretary
• Prof. Olivier Riant (UCLouvain)
• Prof. Stéphane Vincent (Namur Institute of Structured Matter (Unamur), Belgium)
• Prof. Olivier Baudoin (Department of Chemistry University of Basel, Switzerland)

Pay attention :

The public defense of Lei Hu scheduled for Friday 30 October at 15:00 will take place in the form of a video conference Teams

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