Inverse temperature dependent lifetimes of transient S(N)2 ion-dipole complexes.

The association and collisional stabilization of the S(N)2 entrance channel complex [Cl(-)...CH3Cl]* is studied in a low-temperature radiofrequency ion trap. The temperature dependence of the ternary rate coefficient is measured and a much stronger inverse temperature dependence than expected from a simple statistical calculation is found. From these data the lifetime of the transient S(N)2 complex has been derived as a function of temperature. It is suggested that the inverse temperature dependent rates of nonsymmetric S(N)2 reactions are related to the observed inverse temperature dependence of the transient ion-dipole complexes.