The hydridoirida-beta-diketone [IrHCl{(PPh2(o-C6H4CO))(2)H)] (1) reacts with benzylamine (C6H5CH2NH2) to give the hydridoirida-beta-ketoimine [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNCH2C6H5))H}] (2), stabilized by an intramolecular hydrogen bond. 2 reacts with water to undergo hydrolysis and amine coordination giving hydridodiacylamino [IrH(PPh2(o-C6H4CO))(2)(C6H5CH2NH2)] (3). Cydohexylamine or dimethylamine lead to hydridodiacylamino [IrH(PPh2(o-C6H4CO))(2)L] (4-5). In chlorinated solvents hydridodiacylamino complexes undergo exchange of hydride by chloride to afford [IrCl(PPh2(o-C6H4CO))(2)L] (6-9). The reaction of 1 with hydrazine (H2NNH2) gives hydridoirida-beta-ketoimine [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNNH2))H}] (10), fluxional in solution with values for Delta H-double dagger of 2.5 +/- 0.3 kcal mol(-1) and for Delta S-double dagger of -32.9 +/- 3 eu. A hydrolysis/imination sequence can be responsible for fluxionality. 2-Amino-pyridines (RHNC5H3RN) react with 1 to afford cis-[IrCl(PPh2(o-C6H4CO))(PPh2(o-C6H4CHNRC5H3RN))] (R = R' = H (11), R = CH3, R' = H (12), R = H, R' = CH3 (13)) containing new terdentate PCN ligands in a facial disposition and cis phosphorus atoms as kinetic products. The formation of 11-13 requires imination of the hydroxycarbene moiety of 1, coordination of the nitrogen atom of pyridine to iridium, and iridium to carbon hydrogen transfer. In refluxing methanol, complexes 11-13 isomerize to afford the thermodynamic products 14-16 with trans phosphorus atoms. Chloride abstraction from complexes [IrCl(PPh2(o-C6H4CO))(PPh2(o-C6H4CHNRC5H4N))] (R = H or CH3) leads to decarbonylation of the acylphosphine chelating group to afford cationic complexes [Ir(CO)(PPh2(o-C6H4))(PPh2(o-C6H4CHNRC5H4N))]A, 17 (R = H, A = ClO4) and 18 (R = CH3, A = BF4) as a cis/trans = 4:1 mixture of isomers. Single crystal X-ray diffraction analysis was performed on 6, 9, 13, and 14.