The importance of dynamics in simple reactions is made yet again in a recent study by Doubleday and Houk in 1,3-dipolar cycloadditions.1 They looked at the reaction of acetylene or ethylene with either nitrous oxide, diazonioazanide, or methanediazonium. The transition state for these 6 reactions all show a concerted reaction. The transition vector has three major components; (a) symmetric formation/cleavage of the two new σ bonds, (b) bending of the dipolar component, or (c) symmetric bending of the hydrogens of ethylene or acetylene.
Classical trajectories were traced from the transition state back to reactant and forward to product. In the approach of the two fragments, the dipole bend vibrates, but then after the TS, it needs to bend quickly to close the 5-member ring. This means that the bending mode effectively has to “turn a corner” in phase space, and without energy in this mode, the molecules will simple bounce off of each other. Analysis of the reactants indicates significant vibrational excitation of the dipole bending mode.
(1) Xu, L.; Doubleday, C. E.; Houk, K. N., "Dynamics of 1,3-Dipolar Cycloaddition Reactions of Diazonium Betaines to Acetylene and Ethylene: Bending Vibrations Facilitate Reaction," Angew. Chem. Int. Ed. 2009, 48, 2746-2748, DOI: 10.1002/anie.200805906