References

Multidisciplinary

Stabilizing a different cyclooctatetraene stereoisomer

Published in Proceedings of the National Academy of Sciences
Authors Longfei Li, Ming Lei, Yaoming Xie, Henry F. Schaefer, Bo Chen, Roald Hoffmann

Significance Cyclooctatetraene (COT) is a poster child for nonaromatic molecules. An isomer of tub-shaped COT, with one of the ring double bonds changed from the usual cis form to a trans one, lies some 23 kcal/mol higher in energy. Devising a substitution strategy for turning the tables, making the trans isomer the stable point of the system, is the challenge. Simple bonding ideas, of the bulk of substituents, of clamping and turning aromaticity on and off, of pushing electrons in and out of the system, guide us in devising several realistic candidates. Along the way, a set of molecules that might easily split hydrogen reversibly emerges.