The polyfunctional (H)PNX (X=O or N) ligands 1 and 2 react with [Rh(CO) 2 Cl] 2 to give the corresponding chloro carbonyl complexes {Rh[κ 2 -(H)PN](CO)Cl} (1a and 2a), where the neutral ligands coordinate in a κ 2 -PN bidentate fashion, the square planar coordination being completed by the CO trans to N and the chloride trans to P. In chloroform solution 1a maintains its original structure, while 2a partially transforms into the cationic species {Rh[κ 3 -(H)PNO](CO)}Cl. The chloroform solutions of 1a and 2a react with AgPF 6 to give the purely cationic species {Rh[κ 3 -(H)PNO](CO)}PF 6 ([1a] + and [2a] + ), while addition of Et 3 N originates the neutral species {Rh[κ 3 -PNN′](CO)} (1b and 2b). All the complexes have been characterized by microanalysis, IR, 1 H NMR as well as 31 P{ 1 H} NMR spectroscopy. The X-ray structures of ligand 1 and complex 1b are also reported.