Aggregation and ionization equilibria of bis(pentafluorophenyl)borinic acid driven by hydrogen-bonding with tetrahydrofuran

Bis(pentafluophenyl)borinic acid, Ar2BOH (1, Ar = C6F5), in dichloromethane solution is present as an equilibrium mixture of monomeric (1(m)) and trimeric (1(t)) forms. Previous studies showed that water affects both the position and the rate of this equilibrium. Here, the behavior of 1 in the presence of tetrahydrofuran (THF), a nucleophile able to behave as a Lewis base and H-bond acceptor only, has been studied, by monitoring with H-1 and F-19 NMR the course of titrations performed directly into NMR tubes. The addition, at 183 K, of 0.33 equiv of THF caused the instantaneous and quantitative formation of the hydrogen-bonded adduct between the trimer 1(t) and one molecule of THF. Homo- and heteronuclear 2D NMR correlation experiments led to a solution structure consistent with the C-2-optimized geometry obtained by PM3 computations. The H-bonding of the THF molecule causes major deformations of the molecular geometry of the trimer, so that only one molecule of THF can interact with the trimer, in spite of its three OH groups. Intra- and intermolecular exchange processes involving this adduct have been investigated by 2D EXSY experiments, showing flopping of the cycle conformation, rotation of the aromatic rings around their B-C bonds, and exchange of THF among the three OH groups, in addition to the exchange between free 1(t) and the adduct. When the amount of added THF was higher than 0.33 equiv, an unexpected ionization process occurred, leading to the cation [Ar2B(OH2)(2)](+) and to deprotonated 1(t), i.e., to the anion [Ar6B3O3H2](-) of C-s symmetry. On increasing the temperature, progressive partial fragmentation of the trimeric species was observed. Both B-11 NMR evidence and PM3 computations indicated that, at variance with what is observed in the interaction with H2O, the interaction between THF and 1(m) occurs preferentially via an H-bonded adduct, Ar2BO-H center dot center dot center dot THF, rather than a Lewis acid-base complex, Ar2B(OH)(THF). This confirms the poor Lewis acidity of the boron atom of f1(m).