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Issue 21, 2011
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Halogen bonding to a divalent sulfur atom: an experimental study of the interactions of CF3X (X = Cl, Br, I) with dimethyl sulfide

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Abstract

Using FTIR and Raman spectroscopy, the formation of halogen bonded complexes of the trifluorohalomethanes CF3Cl, CF3Br and CF3I with dimethyl sulfide (DMS) dissolved in liquid krypton has been investigated. For CF3Br and CF3I, evidence was found for the formation of C–X⋯S halogen bonded 1  1 complexes. At higher concentrations of CF3I weak absorptions due to a 2  1 complex were also observed. Using spectra recorded at temperatures between 118 and 163 K, the complexation enthalpies for the complexes were determined to be −9.5(5) kJ mol−1 for CF3Br·DMS, −17.4(1) kJ mol−1 for CF3I·DMS and −30.8(16) kJ mol−1 for (CF3I·)2DMS. The results from the cryospectroscopic study are compared with ab initio calculations at the MP2/aug-cc-pVDZ(-PP) level. Apart from vibrational modes localized in the trifluorohalomethanes and the DMS moieties, for both CF3Br and CF3I, an additional band, which we assign as the intermolecular stretching mode in the complex, was identified in the infrared and Raman spectra.

Graphical abstract: Halogen bonding to a divalent sulfur atom: an experimental study of the interactions of CF3X (X = Cl, Br, I) with dimethyl sulfide

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Publication details

The article was received on 23 Dec 2010, accepted on 21 Mar 2011 and first published on 20 Apr 2011


Article type: Paper
DOI: 10.1039/C0CP02960B
Citation: Phys. Chem. Chem. Phys., 2011,13, 10204-10213
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    Halogen bonding to a divalent sulfur atom: an experimental study of the interactions of CF3X (X = Cl, Br, I) with dimethyl sulfide

    D. Hauchecorne, A. Moiana, B. J. van der Veken and W. A. Herrebout, Phys. Chem. Chem. Phys., 2011, 13, 10204
    DOI: 10.1039/C0CP02960B

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