The syntheses of Ir(I) and Ir(III) complexes incorporating the electron-withdrawing pincer ligand (1,3-C₆H₄(CH₂P(CF₃)₂)₂) (^CF₃PCPH) with (PPh₃)₃Ir(CO)H and subsequent chemistry are reported. Under ambient conditions, reaction of 1 equiv. ^CF₃PCPH with (PPh₃)₃Ir(CO)H gave the mono-bridged complex [Ir(CO)(PPh₃)₂(H)]₂(μ-^CF₃PCPH) (1). Reaction of (PPh₃)₃Ir(CO)H with excess ^CF₃PCPH and MeI gave the doubly-bridged complex [Ir(CO)(PPh₃)(H)]₂(μ-^CF₃PCPH)₂ (2), whereas the tetrameric oligomer [Ir(CO)(PPh₃)(H)]₄(μ-^CF₃PCPH)₄ (2-sq) was obtained from a 1 : 1 ligand : metal mixture in benzene in the presence of excess MeI. At higher temperatures (165 °C) the reaction of ^CF₃PCPH with (PPh₃)₃Ir(CO)H afforded the 5-coordinate Ir(I) complex (^CF₃PCP)Ir(CO)(PPh₃) (3). Complex 3 shows mild catalytic activity for the decarbonylation of 2-naphthaldehyde in refluxing diglyme (162 °C).