Four-membered heterocyclic molecules featuring boron and heavy group 14 elements that exhibit both σ-aromatic and π-aromatic properties: a new synthetic target

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 53; no. 35; pp. 14866 - 14874
• Main Authors: Zhang, Zheng-Feng, So, Cheuk-Wai, Su, Ming-Der
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 10.09.2024
• Subjects: Anisotropy; Aromaticity; Boron; Chemical bonds; Chemical equilibrium; Covalent bonds; Density functional theory; Germanium; Lead; Quantum theory; Tin
• ISSN: 1477-9226; 1477-9234; 1477-9234
• DOI: 10.1039/d4dt02002b

In this study, we present a series of theoretically designed B 2 G14G14′ molecules, featuring four-membered-ring heterocycles containing boron and heavy group 14 elements (G14 and G14′ = Si, Ge, Sn, and Pb). Through the use of density functional theory (DFT), natural bond orbital (NBO) analysis, quantum theory of atoms in molecules (QTAIM), and electron localization function (ELF), our studies demonstrate a strong π single bond between the bridgehead G14 and G14′ atoms, with minimal participation from a very weak G14-G14′ σ bond. Additionally, the nucleus independent chemical shift (NICS), anisotropy of current-induced density (ACID), and adaptive natural density partitioning (AdNDP) analyses definitively establish the presence of both σ-aromaticity and π-aromaticity in these inorganic four-membered heterocyclic neutral molecules. Theoretical findings demonstrate that the inorganic four-membered heterocyclic neutral molecules ( B 2 G14G14′ ) display both σ-aromaticity and π-aromaticity.