AN ANTI-TRADITIONAL INTERPRETATION OF THE LFER MECHANISTIC MESSAGE

In the core of the linear free energy relationship paradigm, lies the 'boundedness' assumption. That is, the nature of the transition state is intermediate between that of the reactants and products. An outcome of this assumption is that the fraction of the effect of a perturbation on the kinetics relative to its effect on the equilibrium of the reaction corresponds to the fraction by which the transition state has progressed along the reaction coordinate. Using computational results for the homolysis of MeX and applying the curve-crossing model to the Michael addition reaction it is shown that the 'boundedness' assumption may, in certain cases, be both quantitatively as well as qualitatively wrong.