Modelling fundamental arene-borane contacts: spontaneous formation of a dibromoborenium cation driven by interaction between a borane Lewis acid and an arene π system.

Reaction of 2,6-dimesityl pyridine (L(py)) with BBr(3) leads to the spontaneous formation of the trigonal dibromoborenium cation L(py)·BBr(2)via bromide ejection. Systematic structural and computational studies, and the reactivity displayed by a closely related N-heterocyclic carbene (NHC) donor, reveal the role played by arene-borane interactions in this chemistry. L(py)·BBr(2) features a structurally characterized (albeit weak) electrostatic interaction between the borane Lewis acid and flanking arene π systems.