Borden predicted measurable heavy-atom isotope effects in the ring opening of cyclopropylcarbinyl radical. In my blog post on this paper, I concluded with the line:

Borden hopes that experimentalists will reinvestigate this
problem (and hopefully confirm his predictions).

Well, in a recent paper where Borden collaborates with Singleton, these predictions are confirmed!1

There is a sizable kinetic isotope effect for breaking the ring bond to a 12C over a bond to a 13C atom, up to 16% at -100 °C. The KIE predicted without including tunneling are dramatically below the experimental values, but incorporation of tunneling in the computated KIEs match up with experiment with an error no greater that 0.7%. The Arrhenius plot of ln KIE vs. 1/T shows enhanced isotope effects when tunneling is included, very nice agreement between the experimental and tunneling-corrected KIEs and curvature – all indicative of heavy atom tunneling. Lastly, the ring open product (1-butene) is the observed major product (62%) at -100 °C; the minor product is methylcyclopropane. In the absence of heavy-atom tunneling, 1-butene would be the minor product (28%).


(1) Gonzalez-James, O. M.; Zhang, X.; Datta, A.; Hrovat, D. A.; Borden, W. T.; Singleton, D. A. J. Am. Chem. Soc., 2010, 132, 12548-12549, DOI: 10.1021/ja1055593.


Cyclopropylcarbonyl radical: InChI=1/C4H7/c1-4-2-3-4/h4H,1-3H2

1-butene: InChI=1/C4H8/c1-3-4-2/h3H,1,4H2,2H3