Article révisé par les pairs
Résumé : Simple molecular orbital theory (HMO) is applied to the study of the metal and electrolytic hydrodimerization reaction of acrylonitrile and some related compounds. A mechanism based on the addition of one single electron in the potential determining step of the reduction is proposed. The sites of protonation of the radical anion and of nucleophilic attack on the neutral molecule were predicted by calculating the appropriate localization energies (L- and L+). The nature of the products obtained (hydrodimer or dihydro compound) is discussed in relation to the basic and dissociative properties of the solvent. © 1968.