Controlling Selectivity by Controlling Energy Partitioning in a Thermal Reaction in Solution.

The comparison of experimental and predicted kinetic isotope effects in the α-cleavage of alkoxy radicals is used here to judge the applicability of statistical rate theories. It is found that the governing rate theory and the statistical versus nonstatistical nature of the cleavage depend on the cleavage barrier and how much energy is imparted to the radical. The latter can then be controlled by changing the size of substituents in the system. With a large alkyl group substituent, the vibrational energy of the alkoxy radical is increased, but this energy is not statistically distributed, leading to a lower isotope effect than predicted by statistical theories. The observed isotope effect can be approximately rationalized using a semistatistical localized RRKM model.