Collect. Czech. Chem. Commun. 2005, 70, 1577-1588

Estimation of Resonance Energy from Forced Nonplanar Conformations of Conjugated Molecules

Stanislav Böhma and Otto Exnerb,*

a Department of Organic Chemistry, Institute of Chemical Technology, Prague, 166 28 Prague 6, Czech Republic
b Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague 6, Czech Republic


Energies of 39 derivatives of buta-1,3-diene in the twisted conformation were calculated within the framework of the density functional theory at the B3LYP/6-311+G(d,p) level. By comparing with the same molecules in their natural minimum-energy conformations, a scale of resonance effects of various substituents was obtained and expressed in terms of isodesmic reactions. Comparison with other similar scales revealed that this model is not particularly advantageous, its main shortcoming being the relatively small effect. In any case it confirmed that the scales of resonance effects obtained from different models are only very roughly proportional: the classical model of resonance works well in representative examples but has its clear limitation when unduly extended.

Keywords: Buta-1,3-diene; Inhibited conjugation; Isodesmic reaction; Resonance energy; Substituent effects; Dienes; Chemometrics; DFT; Ab initio calculations.

References: 36 live references.