To determine the nature of the interaction of an acid with a chlorine substitutent in ethylene, we have examined several vinyl chloride complexes.  The rotational spectra of the vinyl chloride-HF and vinyl chloride-HCCH complexes are studied using both chirped pulse and Balle-Flygare Fouier transform microwave spectroscopy in the 6 � 22 GHz region.  Ab initio calculations, the rotational constants, and hyperfine constants support a planar structure for each complex.  Two interactions are present: a hydrogen bond from the acid to the Cl atom in vinyl chloride, and the second between an H atom in vinyl chloride and the nucleophilic portion of the acid.  The binding modes for the two complexes, however, are different: HF binds across the double bond whereas HCCH binds at one end of the double bond.  Theory suggests that for HCl, an acid with intermediate gas-phase strength between HF and HCCH, the vinyl chloride complex adopts yet another motif: a nonplanar structure.

Impact of acid identity on binding mode in gas-phase bimolecular complexes formed between protic acids and vinyl chloride

247th National Meeting (2014)

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