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 journalArticle

5 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

Fingerprint

Cyclopentanes
Diels-Alder reactions
Cycloaddition Reaction
Ketones
ketones
self consistent fields
Theoretical Models
Salts
salts
Water
Chemical activation
interactions
activation
water
Hydrogen
Hydrogen bonds
destabilization
Geometry
hydrogen bonds
optimization

All Science Journal Classification (ASJC) codes

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

Cite this

Theoretical study of salt effects on the diels-alder reaction of cyclopentadiene with methyl vinyl ketone using RISM-SCF theory. / Yoshida, Norio; Tanaka, Hidetsugu; Hirata, Fumio.

In: Journal of Physical Chemistry B, Vol. 117, No. 45, 14.11.2013, p. 14115-14121.

Research output: Contribution to journalArticle

@article{adf568f4e843482b9ff88c1f6a64f166,
title = "Theoretical study of salt effects on the diels-alder reaction of cyclopentadiene with methyl vinyl ketone using RISM-SCF theory",
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.",
author = "Norio Yoshida and Hidetsugu Tanaka and Fumio Hirata",
year = "2013",
month = "11",
day = "14",
doi = "10.1021/jp4091552",
language = "English",
volume = "117",
pages = "14115--14121",
journal = "Journal of Physical Chemistry B",
issn = "1520-6106",
number = "45",

}

TY - JOUR

T1 - Theoretical study of salt effects on the diels-alder reaction of cyclopentadiene with methyl vinyl ketone using RISM-SCF theory

AU - Yoshida, Norio

AU - Tanaka, Hidetsugu

AU - Hirata, Fumio

PY - 2013/11/14

Y1 - 2013/11/14

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84887975238&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84887975238&partnerID=8YFLogxK

U2 - 10.1021/jp4091552

DO - 10.1021/jp4091552

M3 - Article

C2 - 24144235

AN - SCOPUS:84887975238

VL - 117

SP - 14115

EP - 14121

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 45

ER -