The [1,5]-H migration in cyclopentadiene seems like it should be a very ordinary reaction. A molecular dynamics study by Carpenter at first glance appears to confirm this notion.1 Trajectories studies show that the ratio of endo:exo migration is very close to 1:1, suggesting, as expected, statistical behavior. However, inspection of the time dependence of the endo to exo migration shows oscillatory behavior. This oscillation corresponds to the B1 vibration that effectively flips the methylene group through the ring plane and interchanges the exo and endo hydrogens. The hydrogen preferentially migrates from the endo position, with the ring bent by typically 10°, a point far from the computed [1,5]-H migration transition state (which is planar).
Differential damping this B1 vibration should then lead to variable endo:exo ratios, and Carpenter suggests that performing this reaction in the gas phase and in solution with different solvent viscosities should exhibit such a variable ratio. The experiment awaits an experimenter!
Once again the take-home message is that dynamics matter, even in seemingly simple and well-understood processes. Reactions can take place far from the nominal transition state and the consequences can be significant.
(1) Goldman, L. M.; Glowacki, D. R.; Carpenter, B. K., "Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene," J. Am. Chem. Soc. 2011, 133, 5312-5318, DOI: 10.1021/ja1095717