Ab Initio and Density Functional Theory Study of the Geometry and Reactivity of Benzyne, 3-Fluorobenzyne, 4-Fluorobenzyne, and 4,5-Didehydropyrimidine

Abstract

The geometries and reactivity of three intermediates of the aromatic nucleophilic substitution, 3-fluorobenzyne, 4-fluorobenzyne, and 4,5-didehydropyrimidine, are studied using ab initio molecular orbital theory and density functional theory (DFT). As compared to the traditional ab initio methods, all DFT methods clearly assign more triple-bond character to the carbon−carbon bond in the ring on which the addition occurs. Furthermore DFT methods are found to correctly describe reactive intermediates in which electron correlation effects are expected to be large. The reactivity of the three intermediates is studied using the chemical concepts of electronegativity and hardness. The Fukui function was calculated for a nucleophilic attack at different DFT levels and found to be an adequate reactivity descriptor.