The efforts to prepare new MSbF 6 /MSb 2 F 11 (A = In, Cu, Au, Hg) compounds were partly successful. Reaction between InBF 4 and excess SbF 5 in anhydrous hydrogen fluoride (aHF) yields a mixture of InF 3 ·3SbF 5 and unidentified SbF 3 ·xSbF 5 . The attempts to synthesize MSbF 6 /MSb 2 F 11 salts (A = Au, Hg) by controlled reduction of Au(SbF 6 ) 2 or Hg(SbF 6 ) 2 solutions in aHF/SbF 5 by elemental hydrogen, resulted in the precipitation of metallic Au or Hg 2 (Sb 2 F 11 ) 2 . In the reaction of metallic Cu and deficit SbF 5 , the synthesis of CuSbF 6 was achieved. CuSbF 6 , like CuAsF 6 , is a rare example of a Cu(I) compound in a pure fluorine environment.Vibrational spectra of M(II) hexafluoroantimonates (M = Ni, Fe, Co, Cu, Cr, Pd, Ag) were reinvestigated. It was found that many of them originally assigned to M(SbF 6 ) 2 compounds, belong to their mixtures with oxonium salts H 3 OM(SbF 6 ) 3 , H 3 OSbF 6 , and/or H 3 OSb 2 F 11 .Reactions were studied between MF 2 /2AuF 3 (M = Ni, Cu, Ag, Zn, Cd and Hg) and KrF 2 or UV-irradiated elemental fluorine in aHF as solvent at room temperature. On the basis of mass balances, Raman spectroscopy and X-ray powder diffraction analysis it can be concluded that the isolated solids have structures that can be considered in terms of an M(AuF 6 ) 2 formulation. Previously reported syntheses and characterization of M(AuF 6 ) 2 (M = Mg, Ca, Sr, Ba) were reinvestigated. In the case of M = Ba two different AuF6− salts were isolated.Raman spectra of the majority of synthesized metal hexafluoroaurates (M = Ni, Cu, Ag, Zn, Cd, Hg, Mg and Ca) show more bands than expected for regular AuF6− anion, indicating that the salts obtained exhibit relatively strong cation–anion interactions. The Raman spectra of the remaining Sr and Ba salts show the presence of more regular AuF6− octahedra, indicating weak cation–anion interactions.