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Quantum-chemical study on the mechanism of catalytic dimerization of norbornadiene in the presence of hydride nickel(I) complex

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Abstract

[2+2]-Cyclodimerization of norbornadiene to pentacyclic products with exo-trans(cis)-exo structure in the presence of model catalytically active η4-norbornadiene nickel hydride complex was simulated at the DFT/PBE level of theory. According to the calculations, the rate-determining step in the cyclodimerization process is reductive elimination of the metallacycle whose decomposition yields norbornadiene dimer. The formation of cis-dimer is unfavorable for both kinetic and thermodynamic reasons.

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Authors and Affiliations

  1. Lomonosov Moscow State University of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 119571, Russia

    R. S. Shamsiev, A. V. Drobyshev & V. R. Flid

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  1. R. S. Shamsiev
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  2. A. V. Drobyshev
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  3. V. R. Flid
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Correspondence to R. S. Shamsiev.

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Dedicated to Full Member of the Russian Academy of Sciences I.P. Beletskaya on her jubilee

Original Russian Text © R.S. Shamsiev, A.V. Drobyshev, V.R. Flid, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 3, pp. 358–362.

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Shamsiev, R.S., Drobyshev, A.V. & Flid, V.R. Quantum-chemical study on the mechanism of catalytic dimerization of norbornadiene in the presence of hydride nickel(I) complex. Russ J Org Chem 49, 345–349 (2013). https://doi.org/10.1134/S1070428013030056

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  • DOI: https://doi.org/10.1134/S1070428013030056

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