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The influence of exocyclic lone pairs on the bonding and geometry of type A mesoionic rings

The influence of exocyclic lone pairs on the bonding and geometry of type A mesoionic rings Thumbnail


Abstract

Based on structures determined by X-ray crystallography, ab initio MP2 calculations on type A mesoionic rings give geometries in good agreement with observed values. A study of four mesoionic ring systems, each with exocyclic oxygen, nitrogen or carbon groups, shows that the presence and configuration of exocyclic lone pairs significantly influences the geometry and configurational preference. Using a localised bond model and NBO analysis, these effects are rationalised in terms of an anomeric interaction of lone pairs with the antibonding orbitals of adjacent s bonds. In agreement with experiment, similar effects are calculated for pyran-2-imines.

Acceptance Date May 18, 2021
Publication Date Jul 9, 2021
Publicly Available Date Mar 29, 2024
Journal Structural Chemistry
Print ISSN 1040-0400
Publisher Springer Verlag
DOI https://doi.org/10.1007/s11224-021-01798-8
Publisher URL https://link.springer.com/article/10.1007/s11224-021-01798-8#Abs1

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