Understanding Chemical Reactivity: The Case for Atom, Proton and Methyl Transfers

Abstract

The concept of ldquochemical reactivityrdquo assumes that atoms and molecules contain the necessary information to describe their evolution over time as they transform from reactants to products. This concept was useful in the past to rationalize reactivity trends and predict the behavior of new systems. Free-energy relationships have played a central role in this field. However, electronic effects often counter the energetic effects and give rise to ldquoanomaliesrdquo or separate correlations. We discuss a quantification of the concept of ldquochemical reactivityrdquo, emphasizing the role of molecular and electronic factors in Chemistry.