The first 1,3,5-triaza-7-phosphaadamantane (PTA) ligated iridium compounds have been synthesized. The reaction of PTA with [Ir(COD)Cl]2 (COD = 1,5-cyclooctadiene) under a CO atmosphere produces an inseparable mixture of [Ir(PTA)3(CO)Cl] (1) and the PTA analogue of Vaska's compound, [Ir(PTA)2(CO)Cl] (2). Compound 1 and [Ir(PTA)4(CO)]Cl (3) were prepared via ligand substitution reactions of PTA with Vaska's compound, trans-Ir(PPh3)2(CO)Cl, in absolute and 95% ethanol, respectively. Complex 3 crystallizes in the orthorhombic space group Pbca with a = 20.3619(4) Å, b = 14.0345(3) Å, c = 24.1575(5) Å, and Z = 8. Single-crystal X-ray diffraction studies show that 3 has a trigonal bipyramidal structure in which the CO occupies an axial position. This is the first crystallographically characterized [IrP4(CO]+ complex in which the CO is axially ligated. Compound 1 was converted into 3 by ligand substitution with 1 equiv of PTA in water. Interestingly, the reaction of 3 with excess. NaCl did not result in the production of 1, but instead the formation of the dichloro species, [Ir(PTAH)2(PTA)2Cl2]Cl3 (4) (PTAH = protonated PTA). Dissolution of 1 or 3 in dilute HCI produced 4 and a dihydrido species, [Ir(PTAH)4(H)2]Cl5 (5), which were readily separated by inspection due to their different crystal habits. Compound 5 crystallizes in the triclinic space group P1̄ with a = 12.4432(9) Å, b = 12.5921(9) Å, c = 16.3231(12) Å, α = 76.004(1)°, β = 71.605(1)°, γ = 69.177(1)°, and Z = 2. Complex 5 exhibits a distorted octahedral geometry with two hydride ligands in a cis configuration. A rationale consistent with these reactions is presented by consideration of the steric and electronic properties of the PTA ligand.