Thereaction of [Cp^*M(𝜇-Cl)Cl]₂ (M = Rh, Ir) with 2-aminopyridyl based ligands lead to the formation of mononuclear neutral complexes of general formula [Cp^*MCl₂(L)] {where L1= 2-aminopyridine, L2= 2-amino-3-picoline, L3= 2-amino-3-nirtopyridine, and L4= 2-amino-3-pyridine carboxyaldehyde}. The complexes have been characterized by FT-IR, UV-Vis, $^1$H-$^{13}$C NMR and mass spectroscopic methods. X-ray crystallographic studies of the complexes have shown typical piano-stool geometry around the metal centre in which 2-aminopyridyl ligand acts as an N-monodentate ligand and the amino functionality is not involved in metal coordination. The intra/intermolecular arrangement is due to hydrogen bonding.

Pentamethylcyclopentadienyl iridium(III) and rhodium(III) complexes of formulation [(η⁵- C₅Me₅)M{(C₅H₄N) ₂C=NR)}Cl]PF₆ were prepared by the reaction of [MCl2(η⁵-C₅Me₅)] ₂ (M = Ir or Rh) with dipyridyl-N-alkylimine ligands, (C₅H₄N) ₂C=NR (R = Me or Et) in the presence of NH₄PF₆ at room temperature. The reaction also produced an unexpected dipyridyl-NH-ketimine organometallic compound

[(η⁵-C₅Me₅)M {(C₅H₄N) ₂C=NH}Cl]PF6 as minor product when the reaction was performed under refluxing acetonitrile. The NH-ketimine compounds were formed via N-C single bond cleavage of imine ligand resulting in coordination of the transformed ligand, (C5₅H₄N) ₂C=NH to the metal centre. Complexes were obtained as their hexafluorophosphate salts and characterized based on IR, NMR and ESI-MS spectroscopic data. Authenticity of NH-ketimine organometallic compound was established by single crystal X-ray analysis of a representative compound, which crystallized in orthorhombic space group Pbcn and has a pseudo-octahedral geometry around the metal ion.