Molecular tailoring approach as tool for revealing resonance-assisted hydrogen bond: Case study of Z-pyrrolylenones with the NH⋯OС intramolecular hydrogen bond.
| Autor: | Afonin AV; A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of Russian Academy of Sciences, Irkutsk, Russia., Rusinska-Roszak D; Institute of Chemical Technology and Engineering, Poznan University of Technology, Poznan, Poland. |
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| Jazyk: | angličtina |
| Zdroj: | Journal of computational chemistry [J Comput Chem] 2022 Sep 05; Vol. 43 (23), pp. 1596-1607. Date of Electronic Publication: 2022 Jul 19. |
| DOI: | 10.1002/jcc.26960 |
| Abstrakt: | Both the experimental and calculated data reveal that a strong NH⋯OС intramolecular hydrogen bond closing the seven-membered quasi-cycle is formed in the Z-isomers of pyrrolylenones. Comparison of the NH⋯OС intramolecular hydrogen bonds energies in the pyrrolylenones, estimated via the molecular tailoring approach, with the similar data for reference malonaldehydes shows that the resonance-assisted hydrogen bonding occurs in both cases, the hydrogen bond energy being varied mainly within 10-20 kcal/mol. The combined application of function-based and molecular tailoring approaches makes it possible to decompose the NH⋯OС total hydrogen bond energy in the pyrrolylenones into the π- and σ-components. It is established that the contribution of the π-component to the total N(O)H⋯OС hydrogen bond energy in the pyrrolylenones and malonaldehydes is almost the same (6-7 kcal/mol). Comparison of the π-contribution to the total energy of the resonance-assisted hydrogen bonding in the Z-isomer of pyrrolylenones with the energy of the push-pull effect in the E-isomer of pyrrolylenones reveals that the resonance contribution to the total energy of the resonance-assisted hydrogen bond in the former significantly enhances with reference to the net resonance energy in the latter. The appearance of the resonance-assisted hydrogen bond in the pyrrolylenones is possible due to the participation in the interaction of 10 or 14 π-electrons satisfying the Hückel aromaticity rule. (© 2022 Wiley Periodicals LLC.) |
| Databáze: | MEDLINE |
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