Tuning the hyperconjugative aromaticity in Au(iii)-substituted indoliums

Abstract

As a fundamental concept in chemistry, aromaticity has been extended from traditional organics to organometallics. Similarly, hyperconjugative aromaticity (HCA) has also been developed from main group to transition metal systems through the hyperconjugation of the substituents. However, it remains unclear that how the oxidation state of transition metal in the substituents affects the HCA. Herein, we demonstrate via density functional theory calculations that HCA could disappear in indoliums when the Au(I) substituents are changed to the Au(III) ones. By tuning the ligand or cis–trans isomerization, HCA could be regained or enhanced in indoliums containing Au(III) substitutents.