Binding Selectivity Between Diazobenzene and Different Nucleophilic Reagents : Covalent and Noncovalent Interactions

The specific interaction and reaction mechanism between aromatic diazonium salts and nucleophilic reagents have not been fully clarified yet. Within the framework of density functional theory, we calculated the binding sites and reaction coordinates of six different nucleophiles with diazobcnzene. Chemical hardness of the attacking atom is the main descriptor for describing the binding site. Moreover, a quantitative descriptor is proposed to predict the activation energy barrier in terms of local ionization energy and charge distribution. These results are useful to gain insight for understanding the reaction mechanism of reactions involving aromatic diazonium salts and to explore better reaction conditions.