Kinetic and equilibrium lithium acidities of substituted toluenes: semitheoretical Brönsted correlations.

Semitheoretical Brönsted correlations are compared between previously measured experimental rates of hydrogen isotope exchange of substituted toluenes labeled in the α-position and relative equilibrium acidities computed at several theory levels. The Brönsted correlations show less scatter at the Hartree-Fock level than at higher theory levels. This effect is rationalized on the basis of enhanced steric effects in the more constrained structures of the higher theory levels.