Fourier transform microwave spectroscopy and molecular structure of the 1,1-difluoroethylene-hydrogen fluoride...

Fourier transform microwave rotation spectra in the 7-21 GHz region are obtained for the complex formed between 1,1-difluoroethylene and hydrogen fluoride, including the normal isotopomer and two singly substituted (13)C species obtained in natural abundance. Spectra are also obtained for the analogous three species formed using deuterium fluoride. Analysis of the spectra provides rotational and hyperfine constants that are used, in combination with information from the analogous complex, 1,1-difluoroethylene-acetylene, to determine a structure for CH(2)CF(2)-HF. This structure is similar to that obtained for vinyl fluoride-HF [G. C. Cole and A. C. Legon, Chem. Phys. Lett. 400, 419 (2004)] in that a primary, hydrogen bonding interaction exists between the HF donor and a F atom acceptor on the 1,1-difluoroethylene moiety, while a secondary interaction occurs between the F atom on the HF molecule and the H atom cis to the hydrogen-bonded F atom on the substituted ethylene and causes the hydrogen bond to deviate from linearity. A comparison of the structures of 1,1-difluoroethylene complexes with the protic acids HF, HCl, and HCCH demonstrates that the hydrogen bond length increases with decreasing gas-phase acid strength, whereas a comparison of HF complexes with vinyl fluoride, 1,1-difluoroethylene, and 1,1,2-trifluoroethylene indicates that the nucleophilicity of the F atoms decreases with increasing fluorine substitution, but that the secondary interaction length is remarkably similar in all three complexes.