Dipolar cycloadditions and the || big is good rule: a computational study

We analyze the validity of the || big is good rule over a set of different 1,3-dipolar cycloaddition reactions. We consider different factors that could be important in the practical application of this principle, chiefly: intermolecular interactions and geometry reorganization. We observe that while a simple model of the reagent-reagent perturbations suffices to describe charge transfer in these reactions, it fails when applied to the || big is good rule. On the contrary, geometry changes are proven to be of paramount importance and only when they are correctly taken care of the || big is good rule provides accurate predictions.