Microwave Spectrum and Novel Molecular Structure of (Z)-1-Chloro-3,3,3-trifluoropropene-Acetylene.

Abstract

The gas-phase heterodimer formed between (Z)-1-chloro-3,3,3-trifluoropropene and acetylene is investigated using quantum chemistry calculations and observed via chirped-pulse Fourier transform microwave (FTMW) spectroscopy. Subsequent analysis of higher resolution spectra, including those using a sample enriched in H13C13CH, obtained with a Balle-Flygare FTMW spectrometer reveals a novel structure, as predicted by theory, for the complex, in which the acetylene functions as the gas-phase (Lewis) base and the halopropene as the acid. In the equilibrium structure, the acetylene molecule is located perpendicular to the symmetry plane of (Z)-1-chloro-3,3,3-trifluoropropene with the triple bond interacting with the two olefinic hydrogens. Mapped electrostatic potential surfaces suggest that this structure results from a reduction in the nucleophilicity of the halogen atoms as compared to previously studied acetylene halo-olefin complexes and a concomitant increase in the electrophilicity of the hydrogen atoms.