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, GO; Guner, VİLDAN; Houk, KN

doi:10.1021/jp052055z

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

Atıf İçin Kopyala

Jones G., Guner V., Houk K.

JOURNAL OF PHYSICAL CHEMISTRY A, cilt.110, sa.4, ss.1216-1224, 2006 (SCI-Expanded)

Yayın Türü: Makale / Tam Makale
Cilt numarası: 110 Sayı: 4
Basım Tarihi: 2006
Doi Numarası: 10.1021/jp052055z
Dergi Adı: JOURNAL OF PHYSICAL CHEMISTRY A
Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
Sayfa Sayıları: ss.1216-1224
Hacettepe Üniversitesi Adresli: Evet

Özet

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.