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Mechanism of the Grignard reaction in terms of the cluster model of reaction center. A quantum-chemical study

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Abstract

Most probable paths of the classical Grignard reaction between ethyl bromide and Mg31 cluster simulating the reaction center on the surface of metallic magnesium were analyzed in terms of the density functional theory [B3PW91/6-31G(d)]. Principal thermodynamic parameters of the radical reaction path, including the energy of adsorption of oxidant molecules on the cluster, the energy of formation of ethyl radicals, and the energy of their subsequent interaction with the surface, were calculated. The structure corresponding to the true transition state of the Grignard reaction was identified. The low energy of activation of the reaction occurring at the phase boundary (5.1 kcal/mol) indicated that the surface reaction of radical formation cannot be rate-determining.

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Authors and Affiliations

  1. Research Institute of Chemistry, Lobachevskii Nizhni Novgorod State University, pr. Gagarina 23/5, Nizhni Novgorod, 603950, Russia

    S. K. Ignatov, S. V. Panteleev, S. V. Maslennikov & I. V. Spirina

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  1. S. K. Ignatov
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  2. S. V. Panteleev
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  3. S. V. Maslennikov
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  4. I. V. Spirina
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Correspondence to S. K. Ignatov.

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Original Russian Text © S.K. Ignatov, S.V. Panteleev, S.V. Maslennikov, I.V. Spirina, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 12, pp. 1999–2007.

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Ignatov, S.K., Panteleev, S.V., Maslennikov, S.V. et al. Mechanism of the Grignard reaction in terms of the cluster model of reaction center. A quantum-chemical study. Russ J Gen Chem 82, 1954–1961 (2012). https://doi.org/10.1134/S1070363212120080

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  • DOI: https://doi.org/10.1134/S1070363212120080

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