Studies on the Origin of the Stabilizing Effects of Fluorinated Alcohols and Weakly Coordinated Fluorine-Containing Anions on Cationic Reaction Intermediates

Many synthetic methods that use fluorinated alcohols as solvents have been reported, and the fluorinated alcohols have been found to be crucial to the success of these methods. In addition, there have been reports indicating that adding a weakly coordinated fluorine-containing anion, such as BF4 –, PF6 –, or SbF6 –, to fluorinated alcohols can improve yields. The boosting effect of fluorinated alcohols is attributed mainly to hydrogen bond activation. A few studies have suggested that the very polar fluorinated alcohols can stabilize cationic reaction intermediates. However, how they do so and why weakly coordinated fluorine-containing anions improve yields have not been studied in depth. Here, we used quaternary ammonium cations, a quaternary phosphonium cation, and a triaryl-substituted carbocation as models for short-lived cationic intermediates and studied the possible interactions of these cations with fluorinated alcohols and BF4 –, PF6 –, or SbF6 –. On the basis of the results, we propose that the C–F dipoles of fluorinated alcohols and the E–F dipoles (where E is B, P, or Sb) of weakly coordinated fluorine-containing anions stabilized these cations by intermolecular charge–dipole interactions. We deduced that in the same fashion the C–F and E–F dipoles can thermodynamically stabilize cationic reaction intermediates.