title: Halogen bonding to a divalent sulfur atom: an experimental study of the interactions of CF3X (X = Cl, Br, I) with dimethyl sulfide.
abstract: Using FTIR and Raman spectroscopy, the formation of halogen bonded complexes of the trifluorohalomethanes CF(3)Cl, CF(3)Br and CF(3)I with dimethyl sulfide (DMS) dissolved in liquid krypton has been investigated. For CF(3)Br and CF(3)I, evidence was found for the formation of C-XS halogen bonded 1:1 complexes. At higher concentrations of CF(3)I 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 CF(3)Br·DMS, -17.4(1) kJ mol(-1) for CF(3)I·DMS and -30.8(16) kJ mol(-1) for (CF(3)I·)(2)DMS. 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 CF(3)Br and CF(3)I, an additional band, which we assign as the intermolecular stretching mode in the complex, was identified in the infrared and Raman spectra.
authors.affiliation: Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium.
authors.forename: Dieter
authors.initials: D
authors.lastname: Hauchecorne
authors.forename: Alessio
authors.initials: A
authors.lastname: Moiana
authors.forename: Benjamin J
authors.initials: BJ
authors.lastname: van der Veken
authors.forename: Wouter A
authors.initials: WA
authors.lastname: Herrebout
mesh_terms: D006219:Halogens / Q000737:chemistry*; D007726:Krypton / Q000737:chemistry; D008697:Methane / Q000737:chemistry; D008958:Models, Molecular; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D013440:Sulfides / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D013696:Temperature; D013816:Thermodynamics
chemical_list: D006219:Halogens; D013440:Sulfides; D007726:Krypton; D013455:Sulfur; D008697:Methane; C004784:dimethyl sulfide