Diorganometal fluorides can be synthesized by reaction of the corresponding metallanes with synthons like BF 3 (OEt) 2 and Me 3 SnF. A second general synthesis strategy is the fluoridation of diorganometal halides with alkali metal fluorides or silver fluoride. Organometal difluorides of Al, Ga and In are either unknown or can be obtained in special cases only. Arylthallium difluorides are the result of the reaction of arylthallium bis(trifluoroacetates) and alkali or ammonium fluorides. Various types of salts with anions like [R 3 MF] - , [R 2 MF 2 ] - , [RMF 3 ] - and [R 3 MFMR 3 ] - have been synthesized by the treatment of the corresponding educts R 3 M, R 2 MX, RMX 2 with salt-like fluorides. The IR and NMR spectroscopical data and the structural investigation show the mainly ionic character of the metal fluorine bond.