Could π-aromaticity cross an unsaturated system to a fully saturated one?

Authors: 
Shicheng Dong, Jun Zhu*
Journal: 
Chin. Chem. Lett.
Year: 
2024
Volume: 
35
FirstPage-LastPage: 
In Press
Keywords: 
TOC: 
Abstract: 

The classification of π-/σ-aromaticity depends on the electrons with the dominating contributions. Traditionally, π- and σ-aromaticity are used to describe the unsaturated and saturated systems, respectively. Thus, it is rarely reported that π-aromaticity is dominated in a saturated system. Here we demonstrate that π-aromaticity could be dominating in several fully saturated four-membered rings (4MRs), supported by various aromaticity indices including ΔBL, NICS, EDDB, MCI, and AdNDP. The origin of such π-aromaticity in saturated rings could be attributed to an introduction of two additional electrons into the π-type LUMO of the parent neutral species. Our findings represent a novel approach to achieve π-aromaticity into a fully saturated system which has traditionally been dominated by σ-aromaticity.

https://www.sciencedirect.com/science/article/pii/S1001841723009658

Doi: 
10.1016/j.cclet.2023.109214