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Models for boronic acid receptors: a computational structural, bonding, and thermochemical investigation of the HB(OH)2∙H2O∙NH3 and HB(-O-CH2-CH2-O-)∙NH3∙H2O potential energy surfaces

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Abstract

Results of structural and thermochemical calculations involving boronic acid, HB(OH)2, and the corresponding ethylene glycol ester, HB(-O-CH2-CH2-O-), in the presence of explicit NH3 and/or H2O molecules are reported. Calculations were performed in a polarizable continuum model (PCM) water solution and in the gas phase using density functional theory (DFT) and second-order Moller-Plesset perturbation theory (MP2) with the Dunning-Woon aug-cc-pVTZ basis set. Different classes of local minima on the HB(OH)2·NH3·H2O and HB(-O-CH2-CH2-O-)·NH3·H2O potential energy surfaces (PESs) in PCM water solution have been identified: (1) structures with a N→B dative bond, [H3N→BH(OH)2]·H2O, and [H3N→B(H)(-O-CH2-CH2-O-)]·H2O, where the H2O is involved in hydrogen bonding; (2) water-inserted structures involving either a novel O→B dative bond, H3N·H(H)O→BH(OH)2, and H3N···H(H)O→B(H)(-O-CH2-CH2-O-) where the H2O molecule remains essentially intact or lower-energy zwitterionic arrangements in which a water H atom has been transferred to the ammonia, [H4N]+[HO-BH(OH)2]−, and [H4N]+[BH(OH)(-OCH2-CH2-O-)]−; (3) structures where both the NH3 and H2O molecules are exclusively involved in hydrogen bonding. In these simple model systems, arrangements with N→B dative bonds, and some structures with only O···H and N···H hydrogen bonds, are ca. 5–6 kcal/mol lower in energy than either of the corresponding water-inserted structures.

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Authors and Affiliations

  1. Naples, FL, USA

    George D. Markham

  2. Chemistry Department, Eckerd College, St. Petersburg, FL, 33711, USA

    Joseph D. Larkin

  3. Department of Chemistry and Biochemistry, Jefferson University, East Falls Campus, 4201 Henry Avenue, Philadelphia, PA, 19144, USA

    Charles W. Bock

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Markham, G.D., Larkin, J.D. & Bock, C.W. Models for boronic acid receptors: a computational structural, bonding, and thermochemical investigation of the HB(OH)2∙H2O∙NH3 and HB(-O-CH2-CH2-O-)∙NH3∙H2O potential energy surfaces. Struct Chem 32, 607–621 (2021). https://doi.org/10.1007/s11224-020-01701-x

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