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Alabugin IV, Manoharan M, Breiner B, et al. Control of kinetics and thermodynamics of [1,5]-shifts by aromaticity: a view through the prism of Marcus theory. J Am Chem Soc. 2003;125(31):9329-42doi: 10.1021/ja035729x.
Alabugin, I. V., Manoharan, M., Breiner, B., & Lewis, F. D. (2003). Control of kinetics and thermodynamics of [1,5]-shifts by aromaticity: a view through the prism of Marcus theory. Journal of the American Chemical Society, 125(31), 9329-42. https://doi.org/10.1021/ja035729x
Alabugin, Igor V, et al. "Control of kinetics and thermodynamics of [1,5]-shifts by aromaticity: a view through the prism of Marcus theory." Journal of the American Chemical Society vol. 125,31 (2003): 9329-42. doi: https://doi.org/10.1021/ja035729x
Alabugin IV, Manoharan M, Breiner B, Lewis FD. Control of kinetics and thermodynamics of [1,5]-shifts by aromaticity: a view through the prism of Marcus theory. J Am Chem Soc. 2003 Aug 06;125(31):9329-42. doi: 10.1021/ja035729x. PMID: 12889962.
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J Am Chem Soc. 2003 Aug 06;125(31):9329-42. doi: 10.1021/ja035729x.

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

Journal of the American Chemical Society

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

Affiliations

  1. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA. [email protected]

PMID: 12889962 DOI: 10.1021/ja035729x

Abstract

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.

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