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


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Article Info

DATE

1985-05

AUTHORS

V. V. Yakobson, V. M. Geskin, N. M. Klimenko, K. V. Bozhenko, O. N. Temkin

ABSTRACT

Within the framework of the Hartree-Fock-Roothaan Method, using double-ξ 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-C≡CH+H−→[CH3-CH=CH]− (1) CH3-C≡CH+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: HC≡CH+H−→[CH2=CH]−. More... »

PAGES

290-296

References to SciGraph publications

  • 1970-01. Gaussian basis sets for the first and second row atoms in THEORETICAL CHEMISTRY ACCOUNTS
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    http://scigraph.springernature.com/pub.10.1007/bf00523989

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    http://dx.doi.org/10.1007/bf00523989

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