Is It Conjugated or Not? The Theoretical and Experimental Electron Density Map of Bonding in <i>p</i>-CH₃CH₂COC₆H₄-C≡C-C≡C-<i>p</i>-C₆H₄COCH₃CH₂

Abstract

The electron density of p-CH3CH2COC6H4-C≡CC≡C-p-C6H4COCH3CH2 has been investigated on the basis of single-crystal X-ray diffraction data collected to high resolution at 100 K and from theoretical calculations. An analysis of the X-ray data of the diyne showed interesting “liquidity” of electron distribution along the carbon chain compared to 1,2-diphenylacetylene. These findings are compatible with the results of topological analysis of Electron Localization Function (ELF), which has also revealed a larger (than expected) concentration of the electron density at the single bonds. Both methods indicate a clear π-type or “banana” character of a single bond and a significant distortion from the typical conjugated structure of the bonding in the diyne with a small contribution of cumulenic structures.

Keywords

• polyynes
• density map
• single-crystal X-ray diffraction
• theoretical calculations
• electron localization function