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Rearrangements of cyclopentadienyl cyanates, isocyanates and their thio-,seleno-, and telluro-analogs

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Abstract

Dynamic NMR spectroscopy revealed that pentaphenylcyclopentadienyl isoselenocyanate undergoes reversible hetero-Cope rearrangement (ΔG ≠ 408 K ∼ 22 kcal mol−1, C6D5CD3) giving isomeric selenocyanate in which 1,5-sigmatropic shifts of the SeCN group along the perimeter of the cyclopentadiene ring occur (ΔG ≠ 298 K = 16.7 kcal mol−1, C6D5CD3). On the contrary, pentaphenylcyclopentadienyl iso(thio)cyanates Ph5C5NCO and Ph5C5NCS are structurally rigid compounds on the NMR time scale. The energy barrier to the 3,3-shift of the isoselenocyanate group in pentaphenylcyclopentadienyl derivative Ph5C5NCSe (ΔG 298 K ≠ = 17.9 kcal mol−1) caclulated using the B3LYP/6-31G** method is 7.6 kcal mol−1 lower than for the unsubstituted analog H5C5NCSe.

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Authors and Affiliations

  1. Southern Scientific Center of the Russian Academy of Sciences, 41 ul. Chekhova, 344006, Rostov-on-Don, Russian Federation

    G. A. Dushenko, O. I. Mikhailova, I. E. Mikhailov & V. I. Minkin

  2. Research Institute of Physical and Organic Chemistry of the Southern Federal University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation

    R. M. Minyaev

Authors
  1. G. A. Dushenko
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  2. O. I. Mikhailova
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  3. I. E. Mikhailov
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  4. R. M. Minyaev
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  5. V. I. Minkin
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Correspondence to G. A. Dushenko.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1661—1670, August, 2009.

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Dushenko, G.A., Mikhailova, O.I., Mikhailov, I.E. et al. Rearrangements of cyclopentadienyl cyanates, isocyanates and their thio-,seleno-, and telluro-analogs. Russ Chem Bull 58, 1713–1723 (2009). https://doi.org/10.1007/s11172-009-0237-6

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  • DOI: https://doi.org/10.1007/s11172-009-0237-6

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