Theoretical Chemistry Accounts

, Volume 128, Issue 4–6, pp 569–577 | Cite as

A variational transition state theory description of periselectivity effects on cycloadditions of ketenes with cyclopentadiene

  • Juan Manuel Ramírez-Anguita
  • Ricard Gelabert
  • Àngels González-Lafont
  • Miquel Moreno
  • José M. Lluch
Regular Article

Abstract

The reaction of cycloaddition of ketene and cyclopentadiene presents experimentally a competing mechanism where the branching ratio between the Woodward–Hoffmann allowed [4+2] and forbidden [2+2] cycloaddition product is 4.56 at −20 °C, but because the minimum energy path misses the [2+2] product altogether, it has been claimed to lie beyond the scope of transition state theory. In this paper, a variational transition state theory study on this reaction is presented. It is found that the minimum energy path affording the [4+2] product travels through a potential energy plateau very close to the minimum energy path that describes the interconversion between both cycloaddition products, allowing the transfer between both and the direct formation of the forbidden [2+2] product, in this way acting as a means to circumvent the Woodward–Hooffmann rules. Within the domain of the competitive canonical unified statistical theory, a value for the branching ratio in very good agreement with experiment is computed.

Keywords

Variational transition state theory Woodward–Hoffmann rules Non-symmetrical bifurcating surfaces Cycloaddition reaction 

Notes

Acknowledgments

The authors are grateful for financial support from the “Ministerio de Ciencia e Innovación” (project CTQ2008-02403/BQU) and from the “Generalitat de Catalunya” (project 2009SGR409). The use of supercomputer facilities at the “Centre de Supercomputació de Catalunya” (CESCA) is gratefully acknowledged.

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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Juan Manuel Ramírez-Anguita
    • 1
  • Ricard Gelabert
    • 1
  • Àngels González-Lafont
    • 1
  • Miquel Moreno
    • 1
  • José M. Lluch
    • 1
  1. 1.Departament de QuímicaUniversitat Autònoma de BarcelonaBellaterraSpain

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