Bronsted versus Lewis Acid Type Anion Recognition by Arylboronic Acids

Interactions between arylboronic acids and a series of anions as tetrabutylammonium salts in DMSO and MeCN were studied by H-1 and B-11 NMR as well as spectrophotometrically. Boronic acids act as Bronsted acid type receptors through hydrogen bonding with B(OH)(2) hydroxyl groups toward Cl- Br- HSO4- and AcO- but they act as Lewis acid type receptors toward F- and H2PO4- which form tetrahedral adducts with the B(III) center of boronic acids, although there is also evidence for some contribution of hydrogen bonding with these anions. The Hammett plot for the binding constants of AcO- with 3- and 4-substituted phenylboronic acids in DMSO is nonlinear, with a small negative slope for electron-donating and weakly electron-accepting substituents and a large positive slope for strongly electron-accepting substituents. 3-Nitrophenylboronic acid recognizes zwitterions of amino acids in DMSO, and its UV absorption maximum undergoes a significant red shift in the presence of acetate anions, providing a means for sensing anions optically. Arylboronic acids as Bronsted acid type receptors show relatively low sensitivity to solvent polarity and are equally or even more efficient than widely employed proton donors such as ureas or dicarboxamides.