Li6 E5 Li6 : Tetrel Sandwich Complexes with 10-π-Electrons

Angew Chem Int Ed Engl. 2024 Jan 25;63(5):e202317848. doi: 10.1002/anie.202317848. Epub 2023 Dec 27.

Abstract

When (4n +2) π-electrons are located in single planar ring, it conventionally qualifies as aromatic. According Hückel's rule, systems possessing ten π-electrons should be aromatic. Herein we report a series of D5h Li6 E5 Li6 sandwich structures, representing the first global minima featuring ten π-electrons E5 10- ring (E=Si-Pb). However, these π-electrons localize as five π-lone-pairs rather than delocalized orbitals. The high symmetry structure achieved is a direct consequence of σ-aromaticity, particularly favored in elements from Si to Pb, resulting in a pronounced diatropic ring current flow that contributes to the enhanced stability of these systems.

Keywords: Aromaticity; Bonding; Global Minimum; Sandwich; Stability; Ten π-Electrons; Tetrel Chemistry.