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Mechanism of Chlorotriflamidation of Vinylsilanes with N,N-Dichlorotriflamide

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Abstract

The mechanism of the reaction of vinylsilanes with N,N-dichlorotriflamide and the effect of a substituent at the silicon atom on the reaction course and on the charge distribution in substrates and their carbon analogues were studied by DFT method. The C=C bond in vinylsilanes and alkenes is polarized in the opposite way. The reaction proceeds in two stages: chlorination of the substrate with the formation of a chloronium ion, and its opening at the Cβ–Cl bond by the N-chlorotriflamide anion. Transition states of two stages were calculated. The reaction products are hydrolyzed to NH-derivatives; their IR spectra and supramolecular structure, including cyclic and linear dimers, calculated in the gas phase and in a polar medium, were studied.

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Funding

The work was supported by the Russian Science Foundation (grant 22-13-00036) using the equipment of the Baikal Analytical Center for Collective Use of the Siberian Branch of the Russian Academy of Sciences.

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Authors and Affiliations

  1. A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 664033, Irkutsk, Russia

    N. N. Chipanina, L. P. Oznobikhina, I. V. Ushakova & B. A. Shainyan

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  1. N. N. Chipanina
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  2. L. P. Oznobikhina
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  3. I. V. Ushakova
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  4. B. A. Shainyan
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Correspondence to B. A. Shainyan.

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Chipanina, N.N., Oznobikhina, L.P., Ushakova, I.V. et al. Mechanism of Chlorotriflamidation of Vinylsilanes with N,N-Dichlorotriflamide. Russ J Gen Chem 93, 542–547 (2023). https://doi.org/10.1134/S1070363223030106

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