The IR spectra of the products formed when molecular fluorine passed over molybdenum and tungsten (heated to 100-1100 degreesC) and isolated in inert matrices at 12 K were recorded. In the W + F-2 system, the major product was tungsten hexafluoride. For the Mo + F-2 system, bands of MoF6, MoOF4, (MoF5)(3), MoF5, MoF4, and, possibly, MoF3 were identified. The spectra were interpreted with the use of thermodynamic calculations of the equilibrium composition of the gas phase at various temperatures. The structure of metal fluorides of different compositions is discussed