The stability of covalent dative bond significantly increases with increasing solvent polarity.

Rabindranath Lo, Debashree Manna, Maximilián Lamanec, Martin Dračínský, Petr Bouř, Tao Wu, Guillaume Bastien, Jiří Kaleta, Vijay Madhav Miriyala, Vladimír Špirko, Anna Mašínová, Dana Nachtigallová, Pavel Hobza

Journal: Nature communications 2022;13(1):2107

PMID: 35440662

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Abstract

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 MeNBH 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 (ΔE) 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 ΔE. 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.

Address: Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo námĕstí 542/2, 16000, Prague, Czech Republic.; Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute, Palacký University Olomouc, Křížkovského 511/8, 77900, Olomouc, Czech Republic.; Maulana Abul Kalam Azad University of Technology, West Bengal (formerly known as West Bengal University of Technology) Simhat, Haringhata, West Bengal, 741249, India.; 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. [email protected].; IT4Innovations, VŠB-Technical University of Ostrava, 17. listopadu 2172/15, 70800, Ostrava-Poruba, Czech Republic. [email protected].; Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo námĕstí 542/2, 16000, Prague, Czech Republic. [email protected].; IT4Innovations, VŠB-Technical University of Ostrava, 17. listopadu 2172/15, 70800, Ostrava-Poruba, Czech Republic. [email protected].

DOI: 10.1038/s41467-022-29806-3

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MeSH Terms: Ions, Solvents, Thermodynamics