Theory, experiment and unusual features of potential energy surfaces of pericyclic and pseudopericyclic reactions with sequential transition structures

David Martin Birney

Research output: Contribution to journalArticlepeer-review

50 Scopus citations

Abstract

Recent computational and experimental studies of organic reactions that show sequential transition structures on the potential energy surfaces are reviewed. The specific focus is on pericyclic and pseudopericyclic reactions. A distinction is made between symmet-ric and unsymmetric systems; in the former, the intrinsic reaction coordinate connects the two transition structures. The importance of the change in the reaction coordinate for establishing the existence of the second transition structure and the influence of the energy of the second transition structure on the barrier height of the first and emphasized. In this latter context, corners on a reaction pathway are also significant. Lastly, the merging of two sequential transition structures is shown to give an "effective monkey saddle" transition structure.

Original languageEnglish
Pages (from-to)1658-1668
Number of pages11
JournalCurrent Organic Chemistry
Volume14
Issue number15
DOIs
StatePublished - 2010

Keywords

  • Ab initio calculations
  • Bifurcations
  • Bis-pericyclic reactions
  • Density functional calculations
  • Monkey saddle points
  • Nonstatistical effects
  • Pericyclic reactions
  • Potential energy surfaces
  • Pseudopericyclic reactions
  • Reaction path corners
  • Reaction paths
  • Sequential transition states
  • Transition states
  • Transition structures
  • Valley-ridge inflection points

Fingerprint

Dive into the research topics of 'Theory, experiment and unusual features of potential energy surfaces of pericyclic and pseudopericyclic reactions with sequential transition structures'. Together they form a unique fingerprint.

Cite this