Theoretical study of salt effects on the diels-alder reaction of cyclopentadiene with methyl vinyl ketone using RISM-SCF theory

Norio Yoshida, Hidetsugu Tanaka, Fumio Hirata

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)

Abstract

Salt effects on the Diels-Alder reaction of cyclopentadiene with methyl vinyl ketone are investigated using reference interaction site model self-consistent field (RISM-SCF) theory. The rate of the reaction is accelerated by adding LiCl to the water solvent. The structures of four transition states, endo-cis, endo-trans, exo-cis, exo-trans, were found by geometry optimization of the cyclopentadiene and methyl vinyl ketone complexes. The endo-trans structure shows the lowest energy in both water and LiCl solution. The activation barrier of the reaction in LiCl solution is lower than that in water, and the difference is in good agreement with that from experiments. The decrease in the activation barrier arises from destabilization of the reactant species. The salt effect of LiCl makes all species concerning the reaction unstable by the hydrophobic effect; however, the increased hydrophobic effect in the TS complexes is suppressed by making the hydrogen bond, which is stronger compared with the reactant methyl vinyl ketone.

Original languageEnglish
Pages (from-to)14115-14121
Number of pages7
JournalJournal of Physical Chemistry B
Volume117
Issue number45
DOIs
Publication statusPublished - Nov 14 2013

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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