Mechanistic significance of the magnitude of cross‐interaction constants

Abstract

AbstractThe relationship between the magnitude of the cross‐interaction constant, |ρij|, and the force constant of activation, ΔF‡ij, has been derived and their equivalence has been shown, where ΔF‡‡= (force constant in the transition state, ΔF‡ij‐ force constant in the ground state, F0ij). When bond formation is involved in the activation process, ΔF‡ij becomes equal to F‡ij and |ρij| is inversely related to the distance, r‡ij, between reaction centres Ri and Rj. However, for bond‐breaking processes, interpretation of |ρij| becomes complicated, since ΔF‡ij = F‡ij − F0ij may be negative or positive depending on the relative size of F‡ij and F0ij. Some examples of re‐examination are given for various cases of |ρij| in the bond‐breaking processes.