A general synthetic strategy starting from metal alkyls is reported based on the hydrogen difluoride anion as a suitable reagent for obtaining organometallic fluorides. The newly prepared compounds are [Me4N][(i-Bu)(2)AlF2] (1), [Ph4P][(i-Bu)(2)AlF2] (2), and [Ph4P][AlF4] (3), containing the tetrahedral anions [(i-Bu)(2)AlF2](-) and [AlF4](-). The actual structures are prototypes that allowed a comparison of inorganic and organometallic fluorides in the frame of the hard and soft arid and base principle, by means of ab initio calculations. A new theoretical model is designed to put in equation form the qualitative statements of the Bent rule. The model allows the rationalization of the tendencies of bond angle variation in (R2MX2] systems containing a main group metal (M), in terms of hybridization of the central atom and the reciprocal influence of hard and soft ligands.