Comparative Study Of Xo Center Dot Center Dot Center Dot Clf And Xs Center Dot Center Dot Center Dot Clf (X = H, Ch3, And F) Halogen-Bonded Complexes

Quantum chemical calculations have been performed to study the single-electron halogen bonds in HO center dot center dot center dot ClF and HS center dot center dot center dot ClF complexes. The calculation methods have a larger effect on the S center dot center dot center dot Cl halogen bond than on the O center dot center dot center dot Cl one. The interaction strength in HO center dot center dot center dot ClF complex is stronger than that in HS center dot center dot center dot ClF one, but the presence of methyl group in the halogen acceptor makes the sequence reverse. The methyl group has a greater effect on the S center dot center dot center dot Cl halogen bond than on the O center dot center dot center dot Cl one. The charge analyses indicate that the methyl group is electron-donating and the electron-donating role in the H3CS-ClF complex is larger than in the H3CO-ClF one. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 3856-3863, 2011