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

Student thesis: Master typesMaster in Chemistry Research focus

Abstract

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.
Date of Award1 Feb 2019
Original languageEnglish
Awarding Institution
  • University of Namur
SupervisorGuillaume Berionni (Supervisor) & Benoit CHAMPAGNE (Co-Supervisor)

Attachment to an Research Institute in UNAMUR

  • NISM

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