Multiple bond migration with participation of a protophilic agent

The pathways of migration of the multiple bond in propene and propyne molecules involving the hydroxide ion were investigated by theab initio (RHF/6-31+G^* and MP2/6-31+G^*) methods. Stationary points corresponding to stable complexes between the molecules under study and the hydroxide ion and between corresponding carbanions and water molecule were found on the potential energy surfaces of the proton transfer reactions. In the presence of hydroxide ion, migration of the multiple bond can occur by an “intramolecular” mechanism of the proton transfer involving the proton of hydroxide ion bound in the complex with propene or propyne molecule. For the propene system, such a mechanism seems to be quite realistic and more preferable energetically than a traditional two-stage mechanism with a passage of the proton into the medium. For the system with the triple bond, an equal expenditure of energy is required to follow any mechanism (without taking into account the effects of solvation and the interaction with a cation), whereas the formation of the stable [H₂C=C=CH·H₂O]⁻ complex can prevent further transformations. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 35–41, January, 1999.