A reaction of [{Cp*IrCl(mu-Cl)}(2)] (Cp* = eta(5)-C-5(CH3)(5)) with 1-(pyridin-2-yl)ethanone oxime (PyNOH) afforded the cationic oxime complex [Cp*IrCl(PyNOH)]Cl (3) with an acidic OH group at the beta-position to the metal center. Complex 3 underwent reversible deprotonation to give the corresponding oximato complex [Cp*IrCl-(PyNO)] (4), while treatment of 3 with silver triflate in acetonitrile led to the formation of the dicationic complex [Cp*Ir(PyNOH)-(CH3CN)][OTf](2) (5, OTf = OSO2CF3). The detailed structures of 3-5 have been determined by X-ray crystallography.