4.6 Review

Classification of So-Called Non-Covalent Interactions Based on VSEPR Model

Journal

MOLECULES
Volume 26, Issue 16, Pages -

Publisher

MDPI
DOI: 10.3390/molecules26164939

Keywords

valence-shell electron-pair repulsion model; hydrogen bond; sigma-hole bond; pi-hole bond; electron charge shift

Funding

  1. Spanish Government MINECO/FEDER [PID2019-109555GB-I00]
  2. Eusko Jaurlaritza [IT-1254-19]

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The analysis of various interactions mentioned shows that different types of interactions can influence different chemical reactions in chemical and biological processes. However, the fact that the same type of interaction may be classified differently leads to ongoing debates on classification and nomenclature of interactions.
The variety of interactions have been analyzed in numerous studies. They are often compared with the hydrogen bond that is crucial in numerous chemical and biological processes. One can mention such interactions as the halogen bond, pnicogen bond, and others that may be classified as sigma-hole bonds. However, not only sigma-holes may act as Lewis acid centers. Numerous species are characterized by the occurrence of pi-holes, which also may play a role of the electron acceptor. The situation is complicated since numerous interactions, such as the pnicogen bond or the chalcogen bond, for example, may be classified as a sigma-hole bond or pi-hole bond; it ultimately depends on the configuration at the Lewis acid centre. The disadvantage of classifications of interactions is also connected with their names, derived from the names of groups such as halogen and tetrel bonds or from single elements such as hydrogen and carbon bonds. The chaos is aggravated by the properties of elements. For example, a hydrogen atom can act as the Lewis acid or as the Lewis base site if it is positively or negatively charged, respectively. Hence names of the corresponding interactions occur in literature, namely hydrogen bonds and hydride bonds. There are other numerous disadvantages connected with classifications and names of interactions; these are discussed in this study. Several studies show that the majority of interactions are ruled by the same mechanisms related to the electron charge shifts, and that the occurrence of numerous interactions leads to specific changes in geometries of interacting species. These changes follow the rules of the valence-shell electron-pair repulsion model (VSEPR). That is why the simple classification of interactions based on VSEPR is proposed here. This classification is still open since numerous processes and interactions not discussed in this study may be included within it.

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