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Abstract
We observed ring expansion of 1-methylcyclobutylfluorocarbene at 8 kelvin, a reaction that involves carbon tunneling. The measured rate constants were 4.0 × 10−6 per second in nitrogen and 4 × 10−5 per second in argon. Calculations indicated that at this temperature the reaction proceeds from a single quantum state of the reactant so that the computed rate constant has achieved a temperature-independent limit. According to calculations, the tunneling contribution to the rate is 152 orders of magnitude greater than the contribution from passage over the barrier. We discuss environmental effects of the solid-state inert-gas matrix on the reaction rate.
↵* To whom correspondence should be addressed. E-mail: rss{at}unr.edu(R.S.S.); truhlar{at}umn.edu (D.G.T); borden{at}chem.washington.edu(W.T.B.)
