Binary complexes of tertiary amines with phenylacetylene. Dispersion wins over electrostatics

Abstract

The structures of the binary complexes between phenylacetylene and several tertiary amines viz., triethylamine, 1-ethylpiperidine, 1-ethylpiperazine, 1-azabicyclo[2.2.2]octane, and 1,4-diazabicyclo[2.2.2]octane were inferred using infrared-optical double resonance spectroscopy. The IR spectra in the acetylenic C-H stretching region clearly rule out the formation of electrostatic dominated C-H center dot center dot center dot N hydrogen bonded complexes. The IR spectra also point to the fact that all the five tertiary amines interact with the extended pi electron density of the phenylacetylene moiety, leading to the formation of multidentate C-H center dot center dot center dot pi hydrogen bonded complexes. Additionally a very weak electrostatic C-H center dot center dot center dot N hydrogen bond enhances the stability of the complex marginally. The multidentate C-H center dot center dot center dot pi hydrogen bonded complexes are stabilized by a substantial contribution from the dispersion energy.