Anion-Dependent Reactivity of Mono- and Dinuclear Boron Cations.

The dinuclear bis(N-heterocyclic carbene) borane adduct 2 rapidly reacts with tritylium salts at room temperature but the outcome is strongly impacted by the respective counter-ion. Using tritylium tetrakis(perfluoro-tert-butoxy)aluminate affords - depending on the solvent - either the bis(boronium) ion 4 or the hydride-bridged dication 5. In case of tritylium hexafluorophosphate, however, H/F exchange occurs between boron and phosphorus yielding the dinuclear BF adduct 3 along with phosphorus dihydride trifluoride. H/F exchange also takes place when using the mononuclear N-heterocyclic carbene BH adduct 6 and hence provides a facile route to PH F , which is usually synthesized in more complex reaction sequences regularly involving toxic hydrogen fluoride. DFT calculations shed light on the H/F exchange between the borenium ion and the [PF ] counter-ion and the computed mechanism features only small barriers in line with the experimental observations.