σ‐Aromaticity in a Fully Unsaturated Ring

Abstract Aromaticity is one of the most fundamental and fascinating chemical topics, attracting both experimental and theoretical chemists owing to its many manifestations. Both σ‐ and π‐aromaticity can be classified depending on the character of the cyclic electron delocalization. In general, σ‐aromaticity stabilizes fully saturated rings with σ‐electron delocalization whereas the traditional π‐aromaticity describes the π‐conjugation in fully unsaturated rings. Here, we demonstrate a strong correlation between nucleus‐independent chemical shift (NICS) values and extra cyclic resonance energies (ECREs), which are used to evaluate the σ‐aromaticity in an unsaturated three‐membered ring (3MR) of cyclopropene, which were computed by molecular orbital (MO) theory and valence bond (VB) theory, respectively. Further study shows that the fully unsaturated ring in methylenecyclopropene and its metallic analogy is σ‐aromatic. Our findings revolutionize the fundamental knowledge of the concept of σ‐aromaticity, thus opening an avenue to design σ‐aromaticity in other fully unsaturated systems, which are traditionally reserved as the domain of π‐aromaticity.