Regaining the Woodward-Hoffmann rules for chelotropic reactions via conceptual DFT

Pablo Jaque, José V. Correa, Frank De Proft, Alejandro Toro-Labbé, Paul Geerlings

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

Abstract

In our continuous effort to retrieve the Woodward-Hoffmann rules from conceptual density functional theory (DFT), we have examined the last type of pericyclic reactions, i.e., chelotropic reactions. Both the initial hardness response and the dual descriptor have been investigated to predict the allowed and forbidden character for the addition of SO2 to butadiene (4n system) and 1,3,5-hexatriene (4n + 2 system). It is shown that with both electronic descriptors, the conrotatory/ disrotatory mode for the linear and nonlinear mechanisms are retrieved based on a density-only approach, free from consideration of orbital and (or) wave function symmetry. The dual descriptor moreover reveals that stabilizing interactions are presented only for the linear path, which can be considered as an overall favourable mechanism for a chelotropic reaction.

Original languageEnglish
Pages (from-to)858-865
Number of pages8
JournalCanadian Journal of Chemistry
Volume88
Issue number8
DOIs
Publication statusPublished - 1 Aug 2010

Keywords

  • Chelotropic reactions
  • Conceptual DFT
  • Woodward-Hoffmann rules

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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