Control of kinetics and thermodynamics of [1,5]-shifts by aromaticity: A view through the prism of Marcus theory

Igor V. Alabugin*, Mariappan Manoharan, Boris Breiner, Frederick D. Lewis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

129 Scopus citations


The effects of aromatic stabilization on the rates of [1,5]-hydrogen shifts in a series of carbo- and heterocyclic dihydroaromatic compounds were estimated by B3LYP/6-31G** computations. The aromatic stabilization energy of the product is directly translated into increased exothermicity of these reactions. Relative trends for a significant range of endothermic and exothermic [1,5]-shifts with different intrinsic activation energies are reliably described by Marcus theory. The effects of aromaticity or antiaromaticity are very large and can lead to dramatic acceleration or deceleration of [1,5]-hydrogen shifts and even to complete disappearance of the reaction barrier. Not only the activation energy but the shape and position of the reaction barrier can be efficiently controlled by changes in the aromaticity of the products, making these systems interesting models for studying hydrogen tunneling. Marcus theory can also be applied successfully to other pericyclic shifts such as [1,5]-shifts which involve chlorine and methyl transfer.

Original languageEnglish (US)
Pages (from-to)9329-9342
Number of pages14
JournalJournal of the American Chemical Society
Issue number31
StatePublished - Aug 6 2003

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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