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Anion-Dependent Reactivity of Mono- and Dinuclear Boron Cations
Alexander Röther1, James C Farmer1, Flavio L Portwich1
1Institute of Inorganic and Analytical Chemistry (IAAC), Friedrich Schiller University Jena, Humboldtstraße 8, 07743, Jena, Germany.
Abstract:
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 BF3 adduct 3 along with phosphorus dihydride trifluoride. H/F exchange also takes place when using the mononuclear N-heterocyclic carbene BH3 adduct 6 and hence provides a facile route to PH2 F3 , 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 [PF6 ]- counter-ion and the computed mechanism features only small barriers in line with the experimental observations.
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