Aromaticity generally describes a cyclic structure composed of sp2-hybridized carbon or hetero atoms with remarkable stability and unique reactivity. The doping of even one sp3-hybridized atom often damages the aromaticity due to the interrupted electron conjugation. Here we demonstrate the occurrence of an extended hyperconjugative aromaticity (EHA) in a metalated indole ring which contains two gem-diaurated tetrahedral carbon atoms. The EHA-involved penta-aurated indolium shows extended electron conjugation because of dual hyperconjugation.

Hyperconjugation, a weak interaction in organic chemistry, can have a strong effect on aromaticity, leading to the concept of hyperconjugative aromaticity, which was first proposed by Mulliken in 1939. However, most studies are limited to main group chemistry. Here we report the most aromatic and antiaromatic pyrrolium ring by maximizing the hyperconjugation caused by transition metal fragments and the push–pull effect.