Synthesis of sterically hindered phosphatriptycenes and computational investigation of their properties in the context of frustrated lewis pair chemistry

Traduction de l'intitulé de la thèse: Synthèse de phosphatriptycènes encombrés et évaluation par études computationnelles de leurs propriétés pour la préparation de paires de Lewis frustrées
  • Damien Mahaut

Thèse de l'étudiant: Master typesMaster en sciences chimique à finalité approfondie


Frustrated Lewis Pairs (FLPs) consist in sterically hindered Lewis acid and base that cannot form a Lewis adduct because of steric repulsions. These bifunctional systems have been extensively used as transition metal-free catalysts for hydrogenation reactions and small molecules activation (CO2, NO2, …).
The synthesis of new sterically hindered Lewis bases is crucial for the development of new types of FLP catalysts. In this Master thesis, 9-phosphatriptycene derivatives are put forward as promising candidates for this purpose. They are rigid, robust structures with many functionalizable positions and singular stereoelectronic properties. More specifically, we proposed the synthesis of 9-phosphatriptycene substituted in ortho-position relative to the phosphorus in order to increase its steric hindrance.
A novel synthesis of the unsubstituted 9-phosphatriptycene was developed and adapted to the synthesis of chlorosubstituted derivatives (R = Cl, H). The latter can be converted in a number of compounds with various applications, including potential asymmetric catalysis. In addition, a density functional theory investigation of the association of the studied compounds with a
prototypical boron Lewis acid B(C6F5)3 and an analysis of their thermodynamic, structural, and stereoelectronic properties has been undertaken in view of the rational development of a novel type of FLPs.
la date de réponse1 févr. 2019
langue originaleAnglais
L'institution diplômante
  • Universite de Namur
SuperviseurGuillaume Berionni (Promoteur) & Benoit CHAMPAGNE (Copromoteur)

Attachement à un institut de recherche reconnus à l'UNAMUR

  • NISM

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