Heavy-atom tunnelling in benzene isomers: how many tricyclic species are truly stable?

Abstract

The variety of possible benzene isomers may provide a fundamental basis for understanding structural and reactivity patterns in organic chemistry. However, the vast majority of these isomers remain unsynthesized, while most of the experimentally known species are only moderately stable. Consequently, there is a high probability that the theoretically proposed isomers would also be barely metastable, a factor that must be taken into account if their creation in the laboratory is sought. In this work, we studied the kinetic stability of all 73 hypothetical tricyclic benzene isomers, especially focusing on their nuclear quantum effects. With this in mind, we evaluated which species are theoretically possible to synthesize, detect, and isolate. Our computations predict that 26% of the previously deemed stable molecules are completely unsynthesizable due to their intrinsic quantum tunnelling instability pushing for their unimolecular decomposition even close to the absolute zero. Five more systems would be detectable, but they will slowly and inevitably degrade, while seven more supposedly stable systems will break apart in barrierless mechanisms.