Usefulness of the σ‐Aromaticity and σ‐Antiaromaticity Concepts for Clusters and Solid‐State Compounds. Issue 2 (17th October 2017)

• Record Type: Journal Article
• Authors: Popov, Ivan A.; Starikova, Alyona A.; Steglenko, Dmitry V.; Boldyrev, Alexander I.
• Is Part Of: Chemistry. Volume 24:Issue 2(2018)
• Page Start: 292
• Page End: 305
• Publication Date: 2017-10-17
• Subjects: AdNDP -- bond theory -- multiple antiaromaticity -- multiple aromaticity -- σ-antiaromaticity -- σ-aromaticity; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201702035
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: In this Review we present examples of clusters, molecules, and solid‐state compounds, for which the use of σ‐aromaticity and σ‐antiaromaticity concepts is essential for understanding of chemical bonding. We show that the bonding patterns in these σ‐aromatic and σ‐antiaromatic compounds are similar to those of the corresponding π‐aromatic and π‐antiaromatic chemical systems, respectively. Undoubtedly, σ‐aromaticity helps us understand why the high symmetry isomers are the most stable among myriads of other potential structures. We also show that besides systems exhibiting either σ‐ or π‐aromatic features, there are species, which can possess multiple aromaticity/antiaromaticity, or conflicting aromaticity patterns. We believe that the σ‐aromaticity and σ‐antiaromaticity concepts will be helpful in rationalizing chemical bonding, structure, stability, and molecular properties of chemical species in both organic and inorganic chemistry. We hope that they will also be useful for other areas of science such as material science, catalysis, nanotechnology, and biochemistry. Abstract : Understanding chemical bonding : This Review focuses on the usefulness of the concepts of σ‐aromaticity and σ‐antiaromaticity in chemistry: from small clusters to bulky solid‐state compounds. As one of the numerous examples, the counter‐intuitive geometry of the global minimum structure of the Li2 Mg2 cluster is explained using the σ‐aromaticity based on the particular delocalized bonding pattern and energy considerations (see picture).