Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases

A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/ aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH⋯N hydrogen bond and the other one with a X⋯ halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes. © 2008 American Chemical Society.Peer Reviewe