MULTIPLE BOND MIGRATION WITH PARTICIPATION OF A PROTOPHILIC AGENT - 1- AN AB-INITIO QUANTUM-CHEMICAL STUDY OF 1,3-HYDROGEN SHIFT IN PROPENE AND PROPYNE WITH PARTICIPATION OF HYDROXIDE ION

The pathways of migration of tile multiple bond in propene and propyne molecules involving the hydroxide ion were investigated by the ab ini tio (RHF/4-31G) method. Stationary points corresponding to stable comp lexes between the molecules under study and the hydroxide ion and betw een the corresponding carbanions and water were found on the potential energy surfaces of the proton transfer reactions. There are no transi tion states with energies exceeding the energies of the initial reagen ts or those of the end products on the reaction coordinate. Therefore, the expenditure of energy to overcome the barriers is completely comp ensated by the energy gain due to the formation of intermediate comple xes. The direction of multiple bond migration by this mechanism is alm ost 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.