Multiple bond migration with participation of a protophilic agent1. Anab initio quantum-chemical study of 1,3-hydrogen shift in propene and propyne with participation of hydroxide ion

The pathways of migration of the multiple bond in propene and propyne molecules involving the hydroxide ion were investigated by theab initio (RHF/4-31G) method. Stationary points corresponding to stable complexes between the molecules under study and the hydroxide ion and between the corresponding carbanions and water were found on the pontential energy surfaces of the proton transfer reactions. There are no transition states with energies exceeding the energies of the initial reagents or those of the end products on the reaction coordinate. Therefore, the expenditure of energy to overcome the barriers is completely compensated by the energy gain due to the formation of intermedite complexes. The direction of multiple bond migration by this mechanism is almost completely determined by the ratio of the energies of the initial reagents and the end products. Account of the electron correlation and the extension of the basis set do not lead to radical changes in the results.