Wa. Herrebout et al., Carbon-carbon triple bonds as nucleophiles: Adducts of ethyne and propyne with boron trifluoride, J PHYS CH A, 103(38), 1999, pp. 7639-7645
The mid-infrared (4000-400 cm(-1)) spectra of ethyne/BF3 and propyne/BF3 mi
xtures, dissolved in liquefied argon are discussed. In all spectra, the for
mation of a 1:1 van der Waals complex was observed, while at higher concent
rations of BF3 absorption bands of a 1:2 species between propyne and BF3 we
re also observed. Using spectra recorded at several temperatures between 96
and 125 K, the complexation enthalpy Delta H degrees for ethyne . BF3 was
determined to be -9.3(4) kJ mol(-1). For propyne . BF3 and propyne .(BF3)(2
) the Delta H degrees values are -13.2(4) and -19.8(12); kJ mol(-1), respec
tively. For the 1:1 complexes the structures and harmonic vibrational frequ
encies were calculated at the MP2/6-31+G(d) level, while for the 1:2 adduct
similar calculations were carried out at the corresponding RHF level. Usin
g a SCRF/SCLPCM scheme to correct for the solvent influences, and statistic
al thermodynamics to account for the zero-point vibrational and thermal con
tributions, approximate values for the gas-phase complexation energy were o
btained from the experimental enthalpies. The resulting values, -14.3(10) k
J mol(-1) for ethyne . BF3, -18.9(10) kJ mol(-1) for propyne . BF3, -30.5(1
2) kJ mol(-1) for propyne .(BF3)(2), are compared with the ab initio values
.