Thionyl chloride, a polar solvent, has been employed as a medium For ionic reactions between ansolvo-baaes and solvo­acids. Quaternary ammonium chlorides, such as, tetramethylammonium chloride. trimethylphenyhmenonium chloride, trimethylbenzylammonium chloride, dirnethylphenylbenzylammonium chloride and triethylbenzylammonium chloride, react with solutions of titanium tetrachloride, zirconium tetrachloride and stannic chloride in thionyl chloride to yield normal complexes of the general formula: \([R_1-N-R_2]_2 MCl_6\) The complexes of triethylbenzylammonium chloride with the aforementioned acids, which are highly soluble in thionyl chloride, have been separated out by the addition of dry ethyl acetate to the reaction mixture. Formation of the complexes of zirconium tetrachloride with trimethylbenzylarnmoniurn chloride and triethylbenzyl­ammonium chloride has also been studied by the conductometric method.