All of the molecular molybdenum fluorides, MoF to MoF6, have been synthesised from the reaction of thermally evaporated molybdenum atoms with fluorine molecules and atoms, trapped in argon matrices, and characterised by matrix isolation IR spectroscopy in conjunction with DFT calculations. This includes the first spectroscopic characterisation of MoF and MoF2, the latter of which is very bent with a bond angle of ca. 133°, the reassignment of the IR spectral data for trigonal planar MoF3, the observation of tetrahedral MoF4, the assignment of new features to MoF5 which displays a Jahn-Teller distorted trigonal bipyramidal structure, and octahedral MoF6. When the reaction of fluorine molecules and heated molybdenum is allowed to take place, MoF6, MoF4 and (MoF5)3 are observed
