Aluminabenzene‐based Lewis superacids and weakly coordinating anions

Abstract

Quantum‐chemical calculations were used to describe both the acidity of aluminabenzene‐based Lewis acids and stability of aluminabenzene‐based anions. Aluminabenzene itself was found to exhibit greater acidity than antimony pentaflouride, and thus can be qualified as a Lewis superacid. Substitution of the heterocyclic ring with electron withdrawing groups results in formation of extremely strong Lewis superacids. Two of them, namely AlC5Cl5 and AlC5(CN)5 are the strongest Lewis acids described in the literature so far. Whereas, anions formed after the addition of fluoride anion to substituted aluminabenzene‐based Lewis acids, while characterized by somewhat lower electronic stability than the least coordinating anions hitherto known, are considerably more stable in terms of thermodynamic stability (measured by the propensity to electrophile attack). On this account they are expected to act as counterions for the most reactive cations. The proposed Lewis acids may be prone to the isomerization and dimerization, whereas studied anions are expected to be stable with regard to such processes.