Synthesis and Characterization of Poly(hydrogen halide) Halogenates (–I)

Abstract

Herein, we report the synthesis and characterization of a variety of novel poly(hydrogen halide) halogenates (−I). The bifluoride ion, which is known to have the highest hydrogen bond energy of ≈160 kJ mol−1, is the most famous among many examples of [X(HX)n]− anions (X=F, Cl) known in the literature. In contrast, little is known about poly(hydrogen halide) halogenates containing two different halogens, ([X(HY)n]−). In this work we present the synthesis of anions of the type [X(HY)n]− (X=Br, I, ClO4; Y=Cl, Br, CN) stabilized by the [PPh4]+ and [PPN]+ cation. The obtained compounds have been characterized by single-crystal X-ray diffraction, Raman spectroscopy and quantum-chemical calculations. In addition, the behavior of halide ions in hydrogen fluoride was investigated by using experimental and quantum-chemical methods in order to gain knowledge on the acidity of hydrogen halides in HF.