Re‐establishing the Lost Covalency of the Inverted Bond in [1.1.1]Propellane

Abstract

AbstractThe nature of the bridging C−C bond in [1.1.1]propellane has been a topic of much debate, and finally it has been established to be a charge‐shift bond. But the question remains: Can we restore the “lost” covalency of this charge shift bond? Herein we have attempted to investigate the nature of the bridging C−C bond, by replacing the CH2groups at the wing positions with NH, O, and S. Detailed analyses using atoms in molecules (AIM) and electron localization function (ELF) reveal that the bridging bond emerges as a covalent bond upon substitution with S.