A cryospectroscopic study of the van der Waals complexes between vinyl fluoride and boron trifluoride: Evidence for the existence of sigma and pi complexes
Wa. Herrebout et al., A cryospectroscopic study of the van der Waals complexes between vinyl fluoride and boron trifluoride: Evidence for the existence of sigma and pi complexes, J PHYS CH A, 102(49), 1998, pp. 10173-10181
The complexes formed between vinyl fluoride and BF3 have been investigated
by studying the mid-infrared (4000-400 cm(-1)) spectra of solutions of the
compounds. in liquefied argon and in solid argon matrixes. In both types of
spectra, evidence was found for 1:1 van der Waals complexes. Ab initio mol
ecular orbital calculations at the MP2/6-31+G(d) level indicate that the co
mplexation can occur via the fluorine atom, giving rise to a sigma complex,
or via the C=C bond, resulting in a pi complex. From a comparison of the e
xperimental and theoretical frequencies, it was concluded that all complex
bands observed in the spectra of the cryogenic solutions are due to the sig
ma species. In the spectra of the solid matrixes not only bands of the sigm
a complex, but also weak bands due to the pi complex are observed. Using sp
ectra recorded at several temperatures between 97 and 123 K, the complexati
on enthalpy Delta H degrees for the sigma complex in LAr was determined to
be -11.2(3) kJ mol(-1). Using a SCRF/SCIPCM model to correct for the solven
t influences and using statistical thermodynamics to account for zero-point
vibrational and thermal contributions, the gas-phase complexation energy f
or this complex was derived to be -15.2(3) kJ mol(-1).