Experimental Evidence for Heavy-Atom Tunneling in the Ring-Opening of Cyclopropylcarbinyl Radical from Intramolecular ¹²C/¹³C Kinetic Isotope Effects

The intramolecular ¹³C kinetic isotope effects for the ring-opening of cyclopropylcarbinyl radical were determined over a broad temperature range. The observed isotope effects are unprecedentedly large, ranging from 1.062 at 80 °C to 1.163 at −100 °C. Semiclassical calculations employing canonical variational transition-state theory drastically underpredict the observed isotope effects, but the predicted isotope effects including tunneling by a small-curvature tunneling model match well with experiment. These results and a curvature in the Arrhenius plot of the isotope effects support the recently predicted importance of heavy-atom tunneling in cyclopropylcarbinyl ring-opening.