ABINITIO STUDIES OF THE REACTION BETWEEN DIAZONIUM IONS AND WATER

Ab initio calculations, using the 6-31G basis set, were performed in order to study the energetics of the electrophilic attack on water by such diazonium ions as methyl-, ethyl- and fluoroethyldiazonium. For t he first case, an indication of a transition state appears at the Hart ree-Fock level, whereas for the other two, the energy is continuously decreasing from reactants to products. When correlation energy was tak en into account via single-point MP2/6-31G calculations, a deep ion-di pole energy minimum was observed for the methyldiazonium ion followed by a low transition state, whereas the other two did not change their energy pattern. On performing the MP2/6-31G optimization for the meth yl species, the Hartree-Fock results were confirmed, with a slight dis placement of the transition state toward a shorter CO distance.