Pentamethylcyclopentadienyl iridium dihydride complexes [Cp*Ir(H) 2 (PR 3 )]; (PR 3 = PPh 2 Me, PTA) were prepared by reaction of [Cp*IrCl 2 (PPh 2 Me)] and [Cp*IrCl 2 (PTA)], respectively, with an excess of sodium bis(2-methoxyethoxy)aluminium hydride (Red-Al). Protonation of the dihydride [Cp*Ir(H) 2 (PPh 2 Me)] with HBF 4 ·Et 2 O at low temperature gave the classical trihydride complex [Cp*Ir(H) 3 (PPh 2 Me)]BF 4 that displays quantum mechanical exchange coupling. Reaction of [Cp*IrCl 2 (PPh 2 Me)] with CO gave the half-sandwich iridium carbonyl compound [Cp*IrCl(CO)(PPh 2 Me)]Cl which, by reaction with NaBPh 4 , yielded yellow microcrystals of [Cp*IrCl(PPh 2 Me)(CO)]BPh 4 adequate for X-ray diffraction analysis.