A new family of delocalized lipophilic cations containing one to three carbimino, sulfimino and phosphiminino units with Cl-, Br-, HF2-, and Me3SiF2- as counterions has been designed. The compounds synthesized demonstrate high perform a lice and thermal stability in the 'Halex' fluorination reactions. For the first time sulfur tetrachloride pregenerated at -78degreesC was successfully applied in reactions with N-nucleophiles to afford straightforwardly sulfonium chlorides with three S-N bonds. (C) 2003 Elsevier Ltd. All rights reserved.