Iridium(III) and Rhodium(III) compounds of dipyridyl-N-alkylimine and dipyridyl-NH-ketimine: Spectral characterization and crystal structure
Abstract
Pentamethylcyclopentadienyl iridium(III) and rhodium(III) complexes of formulation [( 5-C 5Me 5)M{(C 5 H 4N) 2 C=NR)}Cl]PF 6 were prepared by the reaction of [MCl 2( 5-C 5Me 5)] 2(M = Ir or Rh) with dipyridyl-N-alkylimine ligands, (C 5 H 4N) 2 C=NR (R = Me or Et) in the presence of NH 4 PF 6 at room temperature. The reaction also produced an unexpected dipyridyl-NH-ketimine organometallic compound [( 5-C 5Me 5)M {(C 5 H 4N) 2 C=NH}Cl]PF 6 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, (C 5 H 4N) 2 C=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
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