Anion Recognition by Benzoxaborole

Abstract

The binding types (H-bonding or coordinate) and stability constants for complexes of 11 mono- and di-anions with benzoxaborole (1) were determined by 1H and 11B NMR titrations in DMSO or MeCN. Compared to phenylboronic acid (PBA), 1 is a stronger Lewis acid and a poorer H-bond donor with only one B-OH group, which is expected therefore to recognize anions mostly through the coordinate bonding. This is the case however only with F–, HPO4 2–, and PhPO3 2– anions, which are coordinately bonded to 1, and partially with SO4 2–, which forms only the H-bonded complex with PBA, but both H-bonded and coordinate complexes with 1. The majority of tested anions (AcO–, PhPO3H–, (PhO)2PO2 –, Cl–, and Br–) form H-bonded complexes with both 1 and PBA, whereas H2PO4 – changes the binding mode from coordinate for PBA to H-bonded for 1. The preferable binding type for each anion is confirmed by calculations of DFT-optimized structures of the anion complexes of 1. The preferable binding type can be rationalized considering the effects of the steric hindrance, more significant for the coordinate bonding, and of increased anion basicity, which is favorable for both binding types, but enhances the strength of coordinate bonding more significantly than the strength of H-bonding.

Zwitterion–neutral form equilibria and binding selectivity of pyridineboronic acids

“…A large negative deviation for 17 most probably is due to a steric hindrance effect of the ortho -methylene group manifested also in other interactions with benzoxaborole. 31 The origin of approximately two-fold positive deviations for 1–3 is not clear at the moment, but a possible reason can be a smaller value of K Z for these acids and consequently a larger fraction of the reactive molecular neutral form at pH 6.…”