Anion Recognition by Benzoxaborole

• Published in: Journal of organic chemistry 2022-06, Vol.87 (12), p.7734-7746
• Main Authors: Martínez-Aguirre, Mayte A., Ortega-Valdovinos, Luis Ramón, Villamil-Ramos, Raúl, Yatsimirsky, Anatoly K.
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.2c00324

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.