Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in Diels-Alder reactions

Diana Yepes, Jane S. Murray, Patricia Pérez, Luis R. Domingo, Peter Politzer, Pablo Jaque

Research output: Contribution to journalArticlepeer-review

64 Citations (Scopus)

Abstract

We have computationally compared three Diels-Alder cycloadditions involving cyclopentadiene and substituted ethylenes; one of the reactions is synchronous, while the others are slightly or highly asynchronous. Synchronicity and weak asynchronicity are characterized by the reaction force constant κ(ξ) having just a single minimum in the transition region along the intrinsic reaction coordinate ξ, while for high asynchronicity κ(ξ) has a negative maximum with minima on both sides. The electron localization function (ELF) shows that the features of κ(ξ) can be directly related to the formation of the new C-C bonds between the diene and the dienophile. There is thus a striking complementarity between κ(ξ) and ELF; κ(ξ) identifies the key points along ξ and ELF describes what is happening at those points.

Original languageEnglish
Pages (from-to)6726-6734
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number14
DOIs
Publication statusPublished - 14 Apr 2014

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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