Heavy-Atom Tunneling in the Ring Opening of a Strained Cyclopropene at Very Low Temperatures

The highly strained 1H-bicyclo[3.1.0]-hexa-3,5-dien-2-one 1 is metastable, and rearranges to 4-oxacyclohexa-2,5-dienylidene 2 in inert gas matrices (neon, argon, krypton, xenon, and nitrogen) at temperatures as low as 3K. The kinetics for this rearrangement show pronounced matrix effects, but in a given matrix, the reaction rate is independent of temperature between 3 and 20K. This temperature independence means that the activation energy is zero in this temperature range, indicating that the reaction proceeds through quantum mechanical tunneling from the lowest vibrational level of the reactant. At temperatures above 20K, the rate increases, resulting in curved Arrhenius plots that are also indicative of thermally activated tunneling. These experimental findings are supported by calculations performed at the CASSCF and CASPT2 levels by using the small-curvature tunneling (SCT) approximation.