The reaction of [(η⁶-p-cymene)Ru(μCl)₂Cl₂] with functionalized phosphine viz, diphenyl-2-pyridylphosphine yielded complexes of the type: (a) P-bonded complex [(η⁶-p-cymene)RuCl₂(PPh₂Py)] (1), (b) P-, N-chelated complex [(η⁶-p-cymene)RuCl-(PPh₂Py)]BF₄ (2) and [RuCl₂(PPh₂Py)₂] (3) resulting from the displacement of thep-cymene ligand. These complexes were characterized by¹H NMR,³¹P NMR and analytical data. The structures of complexes1 and2 have been confirmed by single crystal X-ray diffraction study. Complex1 crystallised in triclinic space groupP 1 witha = 10.9403 (3) Å,b= 13.3108 (3) Å,c= 10-5394 (10) Å, α=88.943 (2)°, β = 117.193 (2)°, γ= 113.1680 (10)°, Z=2 andV= 1230.39 (5) ų. The complex2 crystallises in monoclinic space group P2₁ witha = 9.1738 (4) Å,b = 14.0650 (6) s, c = 10.7453 (5) Å, β= 106.809 (1)°, Z = 2 andV= 1327.22 (10) ų

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