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Isomerization of silicenium and germenium ions in the systems C4H11M+ (M = Si, Ge)

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Abstract

Equilibrium structures of the isomers and transition states of their interconversion in the system C4H11M+ (M = Si, Ge) have been obtained at theB3LYP level of theory using the cc-pVTZ basis set. The structures of these stationary points are close for Si and Ge; the most stable isomer in both systems is the tertiary cation (C2H5)(CH3)2M+, the second in energy is complex with ethylene [(CH3)2HM·C2H4]+. The secondary cation (C2H5)2HM+ is third in energy isomer, the height of the barrier of interconversion for these three cations being practically independent on M. However, for M = Ge a substantial decrease in the energy of isomeric forms corresponding to complexes with alkanes is observed. As a result, in the system C4H11Ge+ the fourth in energy is isomer [(C2H5)Ge·C2H6]+ rather than [(C2H5)H2Ge·C2H4]+ as for M = Si. Nevertheless, the height of the barriers for transition into these structures, although decreasing from M = Si to Ge, remain rather high, and the most favorable route of decomposition in both systems is the elimination of ethylene.

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Authors and Affiliations

  1. St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504, Russia

    I. S. Ignat’ev

  2. Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 2, St. Petersburg, 199034, Russia

    D. V. Vrazhnov & T. A. Kochina

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  1. I. S. Ignat’ev
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  2. D. V. Vrazhnov
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  3. T. A. Kochina
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Correspondence to I. S. Ignat’ev.

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Original Russian Text © I.S. Ignat’ev, D.V. Vrazhnov, T.A. Kochina, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 7, pp. 1117–1121.

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Ignat’ev, I.S., Vrazhnov, D.V. & Kochina, T.A. Isomerization of silicenium and germenium ions in the systems C4H11M+ (M = Si, Ge). Russ J Gen Chem 80, 1283–1287 (2010). https://doi.org/10.1134/S107036321007011X

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  • DOI: https://doi.org/10.1134/S107036321007011X

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