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Mechanisms and kinetics of the elementotropic rearrangements of tetrahydro-4,4,8,8-tetramethyl-4,8-disila-sym-indacene

  • Physical Chemistry
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Abstract

The dynamic stereochemistry of silatropic rearrangements of tetrahydro-4,4,8,8-tetra-methyl-4,8-disila-sym-indacene (dimer of 6,6-dimethyl-6-silafulvene), which exists in solution as an equilibrium mixture of two interconverting isomers, was studied. The mechanisms and complete kinetic scheme of rearrangements were established using1H,13C, and29Si 2D quantitative EXSY NMR spectroscopy. It was found that the interconversion and degenerate rearrangements of the observed isomers proceedvia two concurrent pathways due to the formation of different intermediates. The activation parameters of the rearrangements were determined by means of total lineshape analysis of dynamic NMR (DNMR) spectra.

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Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, Vorobévy Gory, 119899, Moscow, Russian Federation

    V. L. Yarnykh, V. I. Mstyslavsky, V. A. Roznyatovskii & Yu. A. Ustynyuk

  2. State Research Institute of Chemistry and Technology of Organoelement Compounds, 38 sh. Enthuziastov, 111123, Moscow, Russian Federation

    N. N. Zemlyanskii & I. V. Borisova

Authors
  1. V. L. Yarnykh
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  2. V. I. Mstyslavsky
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  3. N. N. Zemlyanskii
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  4. I. V. Borisova
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  5. V. A. Roznyatovskii
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  6. Yu. A. Ustynyuk
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1285–1295, July, 1997.

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Yarnykh, V.L., Mstyslavsky, V.I., Zemlyanskii, N.N. et al. Mechanisms and kinetics of the elementotropic rearrangements of tetrahydro-4,4,8,8-tetramethyl-4,8-disila-sym-indacene. Russ Chem Bull 46, 1228–1238 (1997). https://doi.org/10.1007/BF02495918

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  • DOI: https://doi.org/10.1007/BF02495918

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