Diels-Alder reactions of cyclopentadiene and 9,10-dimethylanthracene with cyanoalkenes: The performance of density functional theory and Hartree-Fock calculations for the prediction of substituent effects


Jones G., Guner V., Houk K.

JOURNAL OF PHYSICAL CHEMISTRY A, vol.110, no.4, pp.1216-1224, 2006 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 110 Issue: 4
  • Publication Date: 2006
  • Doi Number: 10.1021/jp052055z
  • Journal Name: JOURNAL OF PHYSICAL CHEMISTRY A
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.1216-1224
  • Hacettepe University Affiliated: No

Abstract

The activation enthalpies for the reactions of cyclopentadiene with ethylene, acrylonitrile, fumaronitrile, maleonitrile, vinylidene cyanide, tricyanoethylene, and tetracyanoethylene have been computed with the Hartree-Fock quantum mechanical method and a variety of density functionals (B3LYP, BPW91, and MPW1K) and compared to classic experimental data obtained by Sauer, Wiest, and Mielert (Chem. Ber. 1964, 97, 3183). Some significant errors in B3LYP activation enthalpies involving cyano groups, especially 3 or 4 cyano groups, have been identified, whereas HF and MPW1K reproduce substituent effects quite accurately.