Calculations Predict That Heavy-Atom Tunneling Dominates Möbius Bond Shifting in [12]- and [16]Annulene.

The contribution of heavy-atom tunneling to reactions of [12]- and [16]annulene was probed using small-curvature tunneling rate calculations. At the CCSD(T)/cc-pVDZ//M06-2X/cc-pVDZ level, tunneling is predicted to account for more than 50% of the rate for Möbius bond shifting and ca. 35% of the rate for electrocyclization in [12]annulene, and over 80% of the rate for Möbius bond shifting in [16]annulene, at temperatures at which these reactions have been observed experimentally.