The reaction of [{(η⁵-C₅Me₅)M(μ-Cl)Cl}₂] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh₂Py) in dichloromethane solvent yield neutral ϰ¹-P-coordinated rhodium and iridium complexes [(η⁵-C₅Me₅)RhCl₂(κ¹-P-PPh₂Py)]3 and [(η⁵-C₅Me₅) IrCl₂(ϰ¹-P-PPh₂Py)]4. Reaction of complexes 1 and 2 with the ligand PPh₂Py in methanol under reflux give bis-substituted complexes such as [(η⁵-C₅Me₅)RhCl(ϰ¹-P-PPh₂Py)₂]⁺5 and [(η⁵-C₅Me₅)IrCl(ϰ¹-P-PPh₂Py)₂]⁺6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η⁵-C₅Me₅)RhCl(ϰ²-P-N-PPh₂Py)]⁺ 7 and [(η⁵-C₅Me₅)IrCl(ϰ²-P-N-PPh₂Py)]⁺8. Neutral ϰ¹-P-coordinated complexes [(η⁵-C₅Me₅)RhCl₂(ϰ¹-P-PPh₂Py)]3 and [(η⁵-C₅Me₅)IrCl₂(ϰ¹-P-PPh₂Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η⁵-C₅Me₅)RhCl(ϰ²-P-N-PPh₂Py)]⁺7 and [(η⁵-C₅Me₅) IrCl(ϰ²-P, N-PPh₂Py)]⁺8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as analytical methods. The molecular structures of the representative complexes [(η⁵-C₅Me₅)RhCl₂(ϰ¹-P-PPh₂Py)]3, [(η⁵-C₅Me₅)IrCl₂(ϰ¹-P-PPh₂Py)]4 and hexafluorophosphate salt of complex [(η⁵-C₅Me₅)IrCl(ϰ²-P-PPh₂Py)₂]⁺6 are established by single-crystal X-ray diffraction methods