TWO NEW COMPLEXES OF MAIN METALS REACTED BY (C4H9)4NF AND PRODUCTS SEPARATED CHARACTERIZED BY ELEMENTAL ANALYSIS AND SPECTROSCOPIC METHODS. ONE OF THEM IS TETRABUTYLAMMONIUM TETRAFLUOROBISMUTATE (III), (C4H9)4N[BIF4], THAT EASILY SYNTHESIZED IN A NEARLY QUANTITATIVE YIELD USING A DIRECT REACTION OF BIF3 AND TETRABUTYLAMMONIUM FLUORIDE. ANOTHER IS TETYRABUTYLAMMONIUM FLUOROTRICHLOROANTIMONATE (III), [(C4H9)4N][SBCL3F], THAT HAS BEEN SYNTHESIZED BY REACTION OF TETRABUTYLAMMONIUM FLUORIDE WITH SBCL3 SALT. THE METHODS COULD BE USED FOR OTHER COMPOUNDS. THE ADVANTAGES OF THE NEW METHOD ARE DISCUSSED. (C4H9)4N[BIF4] AND (C4H9)4N[SBCL3F] WERE STUDIED EXPERIMENTALLY BY IR, UVVISIBLE SPECTROSCOPY.