Abstract
The mechanism of the [2+2+2] cycloaddition of ethyl acrylate to norbornadiene (NBD) catalyzed by Ni0 complexes was modeled in terms of the density functional theory (DFT) at the PBE level. The formation of the first C—C bond between the coordinated NBD and ethyl acrylate molecules is the rate-determining step of the process. The low stereoselectivity of the reaction is due to the close matching of the activation barriers for the formation of exo- and endo-cycloadducts (25.6 and 24.9 kcal mol−1, respectively).
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Dedicated to Academician of the Russian Academy of Sciences M. P. Egorov on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2301–2305, Novemer, 2013.
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Shamsiev, R.S., Flid, V.R. Quantum chemical study of the mechanism of catalytic [2+2+2] cycloaddition of acrylic acid esters to norbornadiene in the presence of nickel(0) complexes. Russ Chem Bull 62, 2301–2305 (2013). https://doi.org/10.1007/s11172-013-0333-5
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DOI: https://doi.org/10.1007/s11172-013-0333-5