Abstract
Within the framework of the ab initio method SCF MO LCAO, using a model potential, the influence of alkali metal cations on the reactivity of the acetylene molecule has been investigated. Activation of acetylene with respect to a nucleophile is favored by a lowering of energy of the vacant π* orbital upon coordination, a change in its form as a consequence of sufficiently free motion of the cation along the triple bond, and stabilization of the transdistorted form of acetylene in the complex. In the acetylene/alkali/DMSO system, the activating capability of cations is related to the ease of replacement of a solvent molecule in the solvate complex of the acetylene molecule, this capability increasing in the series Li < Na< K.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1793–1797, August, 1990.
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Vitkovskaya, N.M., Kobychev, V.B., Matveenko, N.Y. et al. Quantum-chemical investigation of mechanisms of reactions of nucleophilic addition to acetylene. 7. Evaluation of possible interactions in C2H2/MOH/DMSO system. Russ Chem Bull 39, 1624–1627 (1990). https://doi.org/10.1007/BF00961490
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DOI: https://doi.org/10.1007/BF00961490