Electrofugalities of 1,3-Diarylallyl Cations

Heterolysis rate constants k(1) of differently substituted 1,3-diarylallyl halides and carboxylates have been determined in various solvents. The linear free energy relationship log k(1) = s(f)(N-f + E-f) was found to predict the heterolysis rates (log k(1)) of 1,3-diarylallyl derivatives with a standard deviation of 0.26, corresponding to a factor of 1.82 in k(1), and maximum deviation in k(1) of a factor of 5. Some systematic deviations are evident, however. Thus, 1,3-diarylallyl carboxylates always react faster and 1,3-diarylally1 chlorides always react more slowly than calculated by the quoted correlation equation when both types of leaving groups were used to determine the electrofugality parameters Ef. As 1,3-diarylalyl cations are generated faster in solvolysis reactions and also react faster with nucleophiles than benzhydrylium ions of similar thermodynamic stabilities, i.e, Lewis acidities, one can conclude that the reactions involving 1,3-diarylally1 cations proceed with lower intrinsic barriers than those involving benzhydrylium ions. The electrofugality parameters Ef of 1,3-diarylallylium ions determined in this work were combined with the electrophilicity parameters E of the corresponding cations as well as with the results on ion pair dynamics reported in preceding papers for generating the full mechanistic spectrum of 1,3-diarylallyl solvolyses.