The preparation is described of the trifluoromethoxides of the heavier alkali metals, i.e. MOCF, where M = K, Rb, or Cs. These are stable, crystalline, ionic solids made by the reversible reaction of carbonyl fluoride with the appropriate metal fluoride. No trifluoromethoxides could be prepared from lithium, sodium, barium, or thallium(1) fluorides. Factors affecting the relative stability of such compounds are discussed.Trifluoromethanol, CFBOH, is not known, and is generally assumed to be incapable of existence because of the ease with which compounds having a fluorine atom in a position a to a hydroxyl group would eliminate hydrogen fluoride. Because of this unavailability of the parent alcohol, no metallic trifluoromethoxides have hitherto been reported. We now report the preparation of stable, crystalline trifluoromethoxides of the heavier alkali metals, i.e. MOCF3, where RII = K, Rb, or Cs.A consideration of the possible formation of metallic trifluoromethoxides shows a t once that they are likely to be more ionic in nature than the corresponding methoxides. The completely ionic formulation M+[OCFJd would contain the trifluoromethoxide ion, isoelectronic with the fluoroborate ion, BF4-. The charge in the trifluoromethoxide ion rests formally on the oxygen atom, but it would be shared to some extent by the three fluorine atoms because of their greater electronegativity. The distribution of charge over the whole ion achieved in this way should therefore stabilize it, in a manner not possible in the ionic non-fluorinated methoxides of the alkali metals. The stability of a solid ionic trifluoromethoxide would clearly be influenced by the nature of the cation present, since smaller cations, or those with a high ratio of charge to size, would cause greater polarization of the anion and a correspondingly greater tendency towards decomposition to give a fluoride ion and carbonyl fluoride. In other words, the equilibrium:would be displaced to the left by the presence of large cations. An immediate corollary of this suggestion is that by approaching the equilibrium from the direction of formation rather than decomposition one would have available a possible synthetic route to trifluoromethoxides.