Adaptive σ aromaticity in the rhenacyclopropene rings

Abstract

AbstractSpecies generally exhibit one‐state aromaticity either in the lowest singlet state (S0) or the lowest triplet state (T1) according to the Hückel's and Baird's rules. Hence, it is rare for species exhibit two‐state aromaticity in both the S0 and T1 states (termed as adaptive aromaticity), let alone adaptive σ aromaticity. Here, we report adaptive σ aromaticity in unsaturated rhenacyclopropene rings via density functional theory (DFT) calculations. Various aromaticity indices including NICS, ACID, EDDB together with isodesmic reactions support the adaptive σ aromaticity in these rhenacyclopropene rings. As the T1 state of these species is formed by the ππ* excitation, the σ‐aromaticity of these three‐membered rings in the S0 state could hold in the T1 state. In addition, the aromaticity effect of the fused rings is also examined. Our findings expand the family of adaptive σ aromaticity, enriching the metallaaromatic chemistry.