This paper reports the synthesis and chemistry of the unusual late metal fluoride complexes, Cp’Ir-(PMe(3))(Aryl)F [Cp’ = Cp* (C(5)Me(5)), Aryl = Ph (1a); Cp’ = Cp*, Aryl = p-tolyl (1b); Cp’ = Cp(Et) (C(5)Me(4)Et), Aryl = Ph(1c)]. The solid-state structure of Ic has been determined : crystals of 1c are monoclinic, space group P2(1)/c, with a = 9.235(2) Angstrom, b = 12.667(2) Angstrom, c = 17.129(3) Angstrom, beta 104.547(16)degrees, and Z = 4; R = 3.98%, wR = 4.65% for 2859 data for F-2 > 3 sigma(F-2). These complexes exhibit reactivity that is substantially different from that of related Cl, Pr, and I species because of the greater propensity of fluoride ion to dissociate from the Ir center, even in nonpolar solvents. For example, in solution at room temperature, fluoride is slowly displaced from complexes 1 by Lewis bases such as pyridines and phosphines (L); the resulting salts [Cp’Ir(PMe(3))(Aryl)(L)]F (2) exist in equilibrium with the covalent starting materials. This equilibrium Lies well to the left for pyridines and phosphines under anhydrous conditions, but both the rate of establishment and the magnitude of K-eq are increased dramatically by the addition of H2O.