Projets par an
Résumé
A highly bent triarylborane, 9-boratriptycene, was generated in solution by selective protodeboronation of the corresponding tetra-aryl boron ate complex with the strong Brønsted acid HNTf2. The iptycene core confers enhanced Lewis acidity to 9-boratriptycene, making it unique in terms of structure and reactivity. We studied the stereoelectronic properties of 9-boratriptycene by quantifying its association with small N- and O-centered Lewis bases, as well as with sterically hindered phosphines. The resultant Lewis adducts exhibited unique structural, spectroscopic, and photophysical properties. Beyond the high pyramidalization of the 9-boratriptycene scaffold and its low reorganization energy upon Lewis base coordination, quantum chemical calculations revealed that the absence of π donation from the triptycene aryl rings to the boron vacant pz orbital is one of the main reasons for its high Lewis acidity.
langue originale | Anglais |
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Numéro d'article | 10.1002/ange.202003119 |
Pages (de - à) | 12502-12506 |
Nombre de pages | 5 |
journal | Angewandte Chemie |
Volume | 132 |
Numéro de publication | 30 |
Les DOIs | |
Etat de la publication | Publié - 20 juil. 2020 |
Financement
We acknowledge the University of Namur, the Namur Institute of Structured Matter (NISM), and the Fond National de la Recherche Scientifique (FNRS grant F.4513.18 for GB and FRIA PhD grants for A.O. and D.M.) for financial support. We thank the PC 2 technological platform for access to characterization instruments. The calculations were performed on the computers of the Consortium des Équipements de Calcul Intensif and particularly those of the High‐Performance Computing Platform, which are supported by the FNRS‐FRFC, the Walloon Region, and the University of Namur (Conventions No. GEQ U.G006.15, U.G018.19, 1610468, and RW/GEQ2016). We acknowledge Prof. H. Mayr and Dr. A. R. Ofial (LMU University, Munich), Dr. S. Lakhdar (Paul Sabatier University, Toulouse), Prof. A. Krief, and Dr. N. Tumanova for helpful discussions, and Lei Hu for the sample of 9‐phosphatriptycene.
Empreinte digitale
Examiner les sujets de recherche de « Controlled Generation of 9-Boratriptycene by Lewis Adduct Dissociation: Accessing a Non‐Planar Triarylborane ». Ensemble, ils forment une empreinte digitale unique.Projets
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HydrogenActive: Hydrogénation d’alcènes non-activés, d’amides et du dioxyde de carbone par des catalyseurs de type paires de Lewis frustrées
Mahaut, D. (Responsable du Projet), Berionni, G. (Promoteur) & CHAMPAGNE, B. (Co-Promoteur)
1/10/19 → 1/10/23
Projet: Projet de thèse
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CÉCI – Consortium des Équipements de Calcul Intensif
CHAMPAGNE, B. (Responsable du Projet), Lazzaroni, R. (Responsable du Projet), Geuzaine , C. (Co-investigateur), Chatelain, P. (Co-investigateur) & Knaepen, B. (Co-investigateur)
1/01/18 → 31/12/22
Projet: Recherche
Équipement
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Physico-chimie et caractérisation (PC2)
Wouters, J. (!!Manager), Aprile, C. (!!Manager) & Fusaro, L. (!!Manager)
Plateforme technologique Caracterisation physico-chimiquesEquipement/installations: Plateforme technolgique
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Plateforme Technologique Calcul Intensif
Champagne, B. (!!Manager)
Plateforme technologique Calcul intensifEquipement/installations: Plateforme technolgique
Thèses de l'étudiant
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Synthesis of sterically hindered phosphatriptycenes and computational investigation of their properties in the context of frustrated lewis pair chemistry
Mahaut, D. (Auteur), Berionni, G. (Promoteur) & Champagne, B. (Copromoteur), 1 févr. 2019Student thesis: Master types › Master en sciences chimique à finalité approfondie
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