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Molecules 2013, 18(6), 6829-6851; doi:10.3390/molecules18066829

Exploring the C-X…π Halogen Bonding Motif: An Infrared and Raman Study of the Complexes of CF3X (X = Cl, Br and I) with the Aromatic Model Compounds Benzene and Toluene

Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium
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Received: 23 April 2013 / Revised: 29 May 2013 / Accepted: 31 May 2013 / Published: 10 June 2013
(This article belongs to the Special Issue Halogen Bond: Application and Prospect)
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Abstract

The formation of halogen bonded complexes formed between the trifluorohalomethanes CF3Cl, CF3Br and CF3I and the Lewis bases benzene and toluene at temperatures below 150K was investigated using FTIR and Raman spectroscopy. Experiments using liquid krypton as solvent show that for both CF3Br and CF3I substantial fractions of the monomers can be involved in 1:1 complexes. In addition, weak absorptions illustrating the formation of 2:1 complexes between CF3I and benzene are observed. Using spectra recorded at temperatures between 120 and 140 K, observed information on the relative stability was obtained for all complexes by determining the complexation enthalpies in solution. The resulting values for CF3Br.benzene, CF3I.benzene and (CF3I)2.benzene are −6.5(3), −7.6(2) and −14.5(9) kJ mol−1. The values for CF3Br.toluene and CF3I.toluene are −6.2(5) and −7.4(5) kJ mol−1. The experimental complexation enthalpies are compared with theoretical data obtained by combining results from MP2/aug-cc-pVDZ(-PP) and MP2/aug-cc-pVTZ(-PP) ab initio calculations, from statistical thermodynamical calculations and from Monte Carlo Free Energy Perturbation simulations. The data are also compared with results derived for other C-X···π halogen bonded complexes involving unsaturated Lewis bases such as ethene and ethyne. View Full-Text
Keywords: halogen bonding; C-X···p interactions; infrared spectroscopy; Raman spectroscopy; cryosolutions halogen bonding; C-X···p interactions; infrared spectroscopy; Raman spectroscopy; cryosolutions
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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MDPI and ACS Style

Nagels, N.; Hauchecorne, D.; Herrebout, W.A. Exploring the C-X…π Halogen Bonding Motif: An Infrared and Raman Study of the Complexes of CF3X (X = Cl, Br and I) with the Aromatic Model Compounds Benzene and Toluene. Molecules 2013, 18, 6829-6851.

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