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

Gavin O Jones; Vildan A Guner; K N Houk

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

J Phys Chem A. 2006 Feb 2;110(4):1216-24. doi: 10.1021/jp052055z.

Authors

Gavin O Jones¹, Vildan A Guner, K N Houk

Affiliation

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.

PMID: 16435782
DOI: 10.1021/jp052055z

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.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Alkenes / chemistry*
Anthracenes / chemistry*
Computer Simulation*
Cyanides / chemistry*
Cyclopentanes / chemistry*
Nitriles / chemistry*
Quantum Theory*
Thermodynamics

Substances

Alkenes
Anthracenes
Cyanides
Cyclopentanes
Nitriles
9,10-dimethylanthracene