Ab initio calculations of potential energy surface for reaction of nucleophilic addition of H− ion to methylacetylene

Within the framework of the Hartree-Fock-Roothaan Method, using double- basis sets 3-21++G and (6-31-H-G//3-21++G), the minimum energy paths (MEPs) have been calculated for reactions of nucleophilic addition of the hydride ion H^– to the methylacetylene molecule: CH₃-CCH+H^–[CH₃-CH=CH]^– (1) CH₃-CCH+H^–[CH₃-C=CH₂]^– (2). It has been established that the activation energy for reaction (2) is 7.02 kJ/mole lower than for reaction (1). An analysis has been made of the character of electron density distribution along the MEP of each reaction. It has been shown that distortion of geometry of the reactants plays an important role in intensifying the interaction of the frontier orbitals. The reasons for nonfulfillment of Markownikoff's rule for these reactions have been determined. The results from the calculations are compared with calculations reported in the literature for the related reaction of nucleophilic addition of the hydride ion H^– to the acetylene molecule: HCCH+H^–[CH₂=CH]^–.Translated from Teoreticheskaya i Éxperimental'naya Khimiya, Vol. 21, No. 3, pp. 303–309, May–June, 1985.