It is generally expected that a solvent has only marginal effect on the stability of a covalent bond. In this work, we present a combined computational and experimental study showing a surprising stabilization of the covalent/dative bond in Me3NBH3 complex with increasing solvent polarity. The results show that for a given complex, its stability correlates with the strength of the bond. Notably, the trends in calculated changes of binding (free) energies, observed with increasing solvent polarity, match the differences in the solvation energies (ΔEsolv) of the complex and isolated fragments. Furthermore, the studies performed on the set of the dative complexes, with different atoms involved in the bond, show a linear correlation between the changes of binding free energies and ΔEsolv. The observed data indicate that the ionic part of the combined ionic-covalent character of the bond is responsible for the stabilizing effects of solvents.

Department of Physical Chemistry Palacký University Olomouc 17 listopadu 12 771 46 Olomouc Czech Republic

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Flemingovo námĕstí 542 2 16000 Prague Czech Republic

IT4Innovations VŠB Technical University of Ostrava 17 listopadu 2172 15 70800 Ostrava Poruba Czech Republic

Maulana Abul Kalam Azad University of Technology West Bengal Simhat Haringhata West Bengal 741249 India

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc Křížkovského 511 8 77900 Olomouc Czech Republic

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