Wydział Chemii

Wouter A. Herrebout

Roman Szostak

Benjamin J. Van der Veken

2000

Journal of Physical Chemistry A

104

8480-8488

10.1021/jp001677b

Naukowa

Angielski

Artykuł

The formation of weakly bound molecular complexes between methylenecyclopropane (MeCP) and BF₃ dissolved in liquid argon has been investigated using FTIR spectroscopy. Experimental evidence was found for the formation of a 1:1 complex in which the BF₃ moiety binds to the exocyclic CC double bond, whereas at higher concentrations of BF₃, weak absorption bands due to MeCP·(BF₃)₂ were also observed. Using spectra recorded at different temperatures between 105 and 129 K, the complexation enthalpy for the 1:1 complex in liquid argon was determined to be −10.7(3) kJ mol^-1. Structural and spectral information on the complexes was obtained from density functional calculations at the B3LYP/6-311++G(d,p) level. Applying Free Energy Perturbation Monte Carlo calculations to account for the solvent influences and statistical thermodynamics to calculate the zero-point vibrational and thermal influences, the complexation energy for the 1:1 complex was estimated, from the experimental complexation enthalpy, to be −16.0(10) kJ mol^-1. This value is compared with the B3LYP/6-311++G(d,p) complexation energies and with single point energies calculated at the MP2 = full/aug-cc-PVTZ level.

Complexation, Energy, Liquids, Molecular structure, Monomers

https://doi.org/10.1021/jp001677b

https://www.acs.org/content/acs/en.html