The ionic metallocene complexes [Cp*M-2][BPh4] (CP* = C5Me5) of the trivalent 3d metals Sc, Ti, and V were synthesized and structurally characterized. For M Sc, the anion interacts weakly with the metal center through one of the phenyl groups, but for M = Ti and V, the cations are naked. They each contain one strongly distorted Cp* ligand, with one (V) or two (Ti) agostic C-H... M interactions involving the Cp*Me groups. For Sc and Ti, these Lewis acidic species react with fluorobenzene and 1,2-difluorobenzene to yield [CP*M-2(kF-FC6H5)(n)][BPh4] (M = Sc, n = 2; M = Ti, n = 1) and [CP*M-2(k(2)F-1,2-F2C6H4)][BPh4], the first examples of kF-fluorobenzene and k(2)F-1,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(C6F5)(4)](-), both Sc and Ti form [CP*M-2(k(2) F-C6F5)B(C6F5)(3)] contact ion pairs. The nature of the metal-fluoroarene interaction was studied by density functional theory (DFT) calculations and by comparison with the corresponding tetrahydrofuran (THF) adducts and was found to be predominantly electrostatic for all metals studied.