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Molecular structure and conformations of 1-phenyl-1-silacyclohexane from gas-phase electron diffraction and quantum chemical calculations


Molecular structure and conformational behavior of the title compound 1 were studied experimentally by gas-phase electron diffraction (GED–MS) and theoretically (DFT and MP2). Only two of four possible conformers of 1 differing by axial or equatorial location of the phenyl group and the angle of rotation about the Si–CPh bond contribute to the equilibrium; these are the 1-eq conformer with the phenyl ring plane perpendicular to the averaged silacyclohexane plane and the 1-ax conformer with the phenyl ring and Si–C6 bond lying approximately in one plane. The ratio 1-eq:1-ax is 62 (10):38 (10), which is only slightly different from 78:22 in solution. The presence of up to 10 % of 1-ax_orth conformer cannot be excluded either. The corresponding ΔG values are 0.29 and 0.25 kcal mol−1. The GED molecular structure of 1 is nicely reproduced by DFT and MP2 calculations.

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The financial support of this work by the Russian Foundation for Basic Research (Grant 14-03-00923) is greatly acknowledged.

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Correspondence to Bagrat A. Shainyan.

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. The online version of this article contains supplementary material (optimized geometries, energies vibration frequencies, vibration amplitudes, scattering intensities and backgrounds, experimental details), which is available to authorized users. (DOC 1514 kb)

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Shainyan, B.A., Kirpichenko, S.V., Osadchiy, D.Y. et al. Molecular structure and conformations of 1-phenyl-1-silacyclohexane from gas-phase electron diffraction and quantum chemical calculations. Struct Chem 25, 1677–1685 (2014).

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  • 1-Phenyl-1-silacyclohexane
  • Molecular structure
  • Conformational analysis
  • DFT and MP2 calculations