Rotational spectroscopy and molecular structure of 1,1,2-trifluoroethylene and the 1,1,2-trifluoroethylene-hydrogen fluoride complex

Abstract

Fourier transform microwave rotational spectra in the 6-22 GHz region are obtained for the complex formed between 1,1,2-trifluoroethylene and hydrogen fluoride, including the normal isotopomer, the two singly substituted 13C species, and the complex obtained with DF. A unique planar structure for the complex is determined from a combined analysis of the rotational constants derived from the spectra and atomic positions obtained using Kraitchman [Am. J. Phys. 21, 17 (1953)] substitution coordinates. Consistent with this structure, no hyperfine splitting of rotational lines due to the nuclear quadrupole coupling interaction is observed for the D-containing species. Although the primary interaction in the complex is a hydrogen-fluorine hydrogen bond, as is the case for all previously studied Lewis acid-fluoroethylene complexes, the CF2CHF-HF complex adopts a distinctly different geometry in which both the primary and secondary interactions occur between the HF molecule and a F atom and a H atom, respectively, bonded to the same carbon of CF2CHF. The 2.020(41) A hydrogen bond has hydrogen fluoride as the donor and 1,1,2-trifluoroethylene as the acceptor and forms a 109.0(13) degrees C-F...H angle. The secondary interaction between the hydrogen fluoride F atom and the H atom geminal to the acceptor F atom causes the hydrogen bond to deviate 41.6(51) degrees from linearity. Structural comparisons with analogous complexes formed with mono- and difluorinated ethylenes suggest that the primary hydrogen bond strength and the fluoroethylene fluorine atom basicity both decrease with increasing fluorine substitution. In the course of this work, it was necessary to obtain additional rotational spectra for the 1,1,2-trifluroethylene monomer and to improve the precision of the values of the structural parameters for this molecule.