Möbius π-bond shifting has been identified as a mechanism for thermal configuration change in annulenes. Given that heavy atom tunneling plays a role in planar bond shifting in cyclobutadiene, we explored the contribution of heavy-atom tunneling in the Möbius π-bond shifting in [12]- and [16]annulene. Tunneling in these systems would involve all carbons simultaneously. Intrinsic reaction coordinate calculations using BHandHLYP/cc-pVDZ  and M06-2X/cc-pVDZ levels of theory revealed relatively narrow barrier widths and suggested a high probability of tunneling to Möbius π-bond shifting in [12]- and [16]annulene. The results of POLYRATE small curvature tunneling calculations on these annulenes will be presented.<br/>

Computational study of heavy-atom tunneling in the Möbius π-bond shifting in [12]- and [16]annulene

253rd National Meeting (2017)

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