Binary and ternary phenylboronic acid complexes with saccharides and Lewis bases

Cumulative formation constants for the association of three boronic acids (phenylboronic acid and its ortho-anilinomethyl and ortho-benzylaminomethyl derivatives) with four saccharides (fructose, glucose, mannitol, and sorbitol) were determined by potentiometric titration. Similarly, the constants for the formation binary complexes of the three boronic acids with (hydrogen) phosphate, (hydrogen) citrate, or imidazole were determined. Finally, the formation of ternary complexes of the boronic acids, phosphate, citrate or imidazole, and the saccharides were determined based on the determined values of the binary complexes. The previously unrecognized ternary complexes are significant in all systems investigated, and under some solution compositions, they can be the dominant species in solution over a wide pH range. A value of 15-25 kJ mol(-1) was determined for the energy of the B-N interaction in the benzylmethyl derivative based on the relative stabilities of the ternary phosphate complexes of the three boronic acids. The data are used to rationalize the medium dependence of stepwise formation constants and the apparent acidity constants of previous literature reports. (C) 2004 Elsevier Ltd. All rights reserved.