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Models for boronic acid receptors II: a computational structural, bonding, and thermochemical investigation of the RB(OH)2∙H2O∙NH3 and RB(−OCH2CH2O−)∙NH3∙H2O potential energy surfaces (R = H, methyl, phenyl, and ortho-methyl-phenyl)

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Abstract

Boronic acids and their conjugate esters have been employed in a variety of biomedical applications. This work reports structural, bonding, and thermochemical calculations for the boronic acids, RB(OH)2 (R = H, methyl, phenyl, and ortho-methyl-phenyl) and the corresponding ethylene glycol diesters, RB(−OCH2CH2O−), in the presence of explicit NH3 and/or H2O molecules. Calculations were performed in vacuo and in polarizable continuum model (PCM) aqueous media using density functional theory (DFT) and second-order Moller-Plesset perturbation theory (MP2) with the Dunning-Woon aug-cc-pVTZ basis set. These results quantify the relative stability of N→B dative-bonded, water-inserted Owater→B (Ow→B) dative-bonded, Zwitterionic, and hydrogen-bonded conformers on the model RB(OH)2⋅NH3⋅H2O and RB(−OCH2CH2O−)⋅NH3⋅H2O potential energy surfaces (PESs). In the PCM aqueous media model, conformers containing an H3N→B dative bond and a water molecule bridging the NH3 and acid/ester moieties were found consistently to be lower in energy than arrangements with either a H3N⋯H(H)Ow→B linkage or Zwitterionic forms, [H4N]+[HOw−BR(OH)2]− or [H4N]+[HOw−BR(−OCH2CH2O−)]−. For the acids, however, conformers with a H3N⋯HOwH moiety hydrogen bonded to the boronate hydroxyl group(s) proved to be lowest in energy.

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Cartesian coordinates for all structures, NBO analysis output, and additional figures are available in the Supplementary Materials section.

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Authors and Affiliations

  1. Naples, 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, 4201 Henry Avenue, East Falls CampusPhiladelphia, PA, 19144, USA

    Hossein Rostami & Charles W. Bock

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C.W.B., G.D.M., H.R., and J.D.L. prepared the manuscript along with the accompanying figures. All authors have reviewed and approved the manuscript for submission.

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Markham, G.D., Rostami, H., Larkin, J.D. et al. Models for boronic acid receptors II: a computational structural, bonding, and thermochemical investigation of the RB(OH)2∙H2O∙NH3 and RB(−OCH2CH2O−)∙NH3∙H2O potential energy surfaces (R = H, methyl, phenyl, and ortho-methyl-phenyl). Struct Chem 34, 1951–1972 (2023). https://doi.org/10.1007/s11224-023-02131-1

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