In liquid sulfur dioxide solution, halide ions are specifically solvated so as to form halosulfinate ions. The halosulfinate ions also exist in other aprotic solvents and can be found in the well-known "solvates" which are isolated from liquid SO, solutions. The chloro-, bromo-, and iodosulfinate ions are highly colored due to an internal charge-transfer transition.Vibrational spectra of the XSOa~ions are consistent with the expected pyramidal (C) geometry. The results of an approximate normal-coordinate analysis as well as the relative intensities of the electronic transitions suggest the magnitude of the X--SOa interaction to be in the order FSO2-> CISO2" < BrSCb-< ISO,-. It is apparent that the nature of the halide-sulfur dioxide interaction is obscured by solvation effects in solvents such as acetonitrile and dimethyl sulfoxide. The formation of halosulfinate ions probably plays a significant role in the chemistry of ionogenic halides in liquid SO2.
Raman spectra (50–4000 cm−1) of the gaseous, liquid, and solid phases along with gas-phase infrared spectra (200–4000 cm−1) of four isotopic species of bromochlorofluoromethane HCBr35ClF, HCBr37ClF, DCBr35ClF, and DCBr37ClF have been observed. Data from all three phases were needed to make a detailed vibrational assignment since Fermi resonance enhancement of several overtone and combination modes results in a rather complex spectrum. Twenty-four distinct gas-phase frequencies were used to calculate a generalized valence force field (GVFF) using structural parameters obtained from gas-phase electron diffraction data.
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