Isokinetic relationships for S_NAr reactions in different solvents

Abstract

On the basis of the changes of the activation parameters dΔH 6 ¼ int and dΔS 6 ¼ and the statistically significant isokinetic and compensation temperatures, T iso and T comp , for the S N Ar reactions of the benzene derivatives with anionic and neutral nucleophiles at their structural variations in different solvents, the general isokinetic relationship dΔH 6 ¼ int versus (T iso À T comp ) Á dΔS 6 ¼ was found. The existence of this isokinetic relationship for a series of S N Ar reactions suggests the possibility to predict the T iso value or to interpret it when it is experimentally determined.

Simple method for determining of the isokinetic temperature value for the SNAr reactions in solution

“…The calculations were performed using the original isokin program . All details of the statistical parameters of the IKR for the reaction series of entries 5, 6, 8, 10, and 11 are given in Table S1 of the supporting information.…”

“…Recently, it was shown the possibility to predict the isokinetic temperature T iso based on the variation in the internal enthalpy of activation, δ∆ H ≠ int , and also in the parameters δ∆ S ≠ and δ∆ G ≠ for the S N Ar reactions of the benzene derivatives at structural changes to the nucleophiles and substrates (Equation ) …”