Russian Chemical Bulletin

, Volume 58, Issue 8, pp 1713–1723 | Cite as

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

  • G. A. Dushenko
  • O. I. Mikhailova
  • I. E. Mikhailov
  • R. M. Minyaev
  • V. I. Minkin
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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.

Key words

cyclopentadiene iso(thio,seleno)cyanate sigmatropic shifts dynamic NMR spectroscopy quantum chemical calculations density functional theory B3LYP/6-31G** method 
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Copyright information

© Springer Science+Business Media, Inc.  2009

Authors and Affiliations

  • G. A. Dushenko
    • 1
  • O. I. Mikhailova
    • 1
  • I. E. Mikhailov
    • 1
  • R. M. Minyaev
    • 2
  • V. I. Minkin
    • 1
  1. 1.Southern Scientific Center of the Russian Academy of SciencesRostov-on-DonRussian Federation
  2. 2.Research Institute of Physical and Organic Chemistry of the Southern Federal UniversityRostov-on-DonRussian Federation

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