4.8 Article

Taming the Lewis Superacidity of Non-Planar Boranes: C-H Bond Activation and Non-Classical Binding Modes at Boron

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 7, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202112342

Keywords

boranes; main group chemistry; Lewis acids; organoboron compounds; superacidic systems

Funding

  1. University of Namur
  2. Namur Institute of Structured Matter (NISM)
  3. Fond National de la Recherche Scientifique (FRS-FNRS) [F.4513.18, T.0012.21, GEQ U.G006.15, GEQ U.G018.19, RW/GEQ2016, 1610468, 1.E.097.20, 1.E.086.20, 1.B.087.21F]
  4. FNRS-FRFC
  5. Walloon Region

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This study reveals the rational design and remarkable reactivity of a geometrically constrained boron Lewis superacid. It demonstrates the formation of non-classical electron deficient B-H-B type of bonding and enables challenging chemical transformations through the taming of pyramidal Lewis acid electrophilicity.
The rational design of a geometrically constrained boron Lewis superacid featuring exceptional structure and reactivity is disclosed. It enabled the formation of non-classical electron deficient B-H-B type of bonding, which was supported by spectroscopic and structural parameters as well as computational studies. Taming the pyramidal Lewis acid electrophilicity through weak coordinating anion dissociation enabled a series of highly challenging chemical transformations, such as Csp(2)-H and Csp(3)-H activation under a frustrated Lewis pair regime and the cleavage of Csp(3)-Si bonds. The demonstration of such rich chemical behaviour and flexibility on a single molecular compound makes it a unique mediator of chemical transformations generally restricted to transition metals.

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