Heavy-atom tunneling in semibullvalenes

Abstract

The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene $\bf {2 a}$ and 3,7-dicyano-1,5-dimethylsemibullvalene $\bf {2 b}$ were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in $\bf {2 a}$ and $\bf {2 b}$, two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of $\bf {2 b}$ in cryogenic matrices were found to be smaller than the ones of $\bf {2 a}$ under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of $\bf {2 b}$ compared to that of $\bf {2 a}$ results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for $\bf {2 a}$ in a qualitatively different way than for $\bf {2 b}$