The Antiaromatic Nucleophilic Substitution Reaction (S_NAAr) in Cycloheptatrienyl-Anion Containing Zwitterions with a Möbius-Aromatic Intermediate

Abstract

Antiaromatic nucleophilic substitution reactions in cycloheptatrienide pyridinium and phosphonium zwitterions with initial formation of a cycloheptatetraene intermediate are explored. The mechanism was supported by quantum chemical calculations, first-order reaction kinetics, and high-resolution mass spectrometry. The pyridinium zwitterion exhibited weak antiaromaticity, whereas the intermediate displayed Mobius aromaticity, as evidenced by nuclear independent chemical shift values and the shape of its HOMO. This study represents the eighth confirmed instance of a Mobius-aromatic organic species in its ground state.