Abstract
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 [Me(4)N][(i-Bu)(2)AlF(2)] (1), [Ph(4)P][(i-Bu)(2)AlF(2)] (2), and [Ph(4)P][AlF(4)] (3), containing the tetrahedral anions [(i-Bu)(2)AlF(2)](-) and [AlF(4)](-). The actual structures are prototypes that allowed a comparison of inorganic and organometallic fluorides in the frame of the hard and soft acid 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 [R(2)MX(2)] systems containing a main group metal (M), in terms of hybridization of the central atom and the reciprocal influence of hard and soft ligands.
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