Controlled Generation of 9-Boratriptycene by Lewis Adduct Dissociation: Accessing a Non‐Planar Triarylborane

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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 originaleAnglais
Numéro d'article10.1002/ange.202003119
Pages (de - à)12502-12506
Nombre de pages5
journalAngewandte Chemie
Volume132
Numéro de publication30
Les DOIs
Etat de la publicationPublié - 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.

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