Abstract
Dynamic NMR has revealed intramolecular migrations of hydrogen atom over the periphery of the five-membered ring in 5-(p-tolyl)-1,2,3,4-tetraphenylcyclopentadiene in a deuteronitrobenzene solution with energy barrier ΔG ≠180 = 24.8 kcal/mol. Quantum-chemical DFT calculations B3LYP/6-311++G** have shown that such migrations in 1,2,3,4,5-pentaphenylcyclopentadiene in the gas phase occur in a chiral conformation of propeller type by the mechanism of 1,5-sigmatropic hydrogen shifts with retention of configuration through asymmetric transition state with energy barrier ΔE ≠ ZPE = 25.9 kcal/mol. Enantiomers P and M can readily interconvert into each other (ΔE ≠ ZPE = 3.9 kcal/mol) owing to synchronous flip rotations of the phenyl groups.
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Original Russian Text © G.A. Dushenko, I.E. Mikhailov, O.I. Mikhailova, R.M. Minyaev, V.I. Minkin, 2016, published in Doklady Akademii Nauk, 2016, Vol. 471, No. 4, pp. 433–438.
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Dushenko, G.A., Mikhailov, I.E., Mikhailova, O.I. et al. Sigmatropic hydrogen shifts in aryltetraphenylcyclopentadienes. Dokl Chem 471, 350–355 (2016). https://doi.org/10.1134/S0012500816120028
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DOI: https://doi.org/10.1134/S0012500816120028