Amido-bridged dinuclear rhodium(I) complexes by deprotonation of mononuclear rhodium(I) amine complexes

The preparation of a series of new amido bridged binuclear complexes [(NNN)RhI 2(cod)2] (cod=Z,Z-1,5-cyclooctadiene), [(NNN)RhI 2(hed)2] (hed=1,5-hexadiene) and [(NNN)RhI 2(CO)4] is reported. These complexes contain chelating imidazoleamidoimidazole, pyridineamidopyridine and pyridineamidopyrrolate ligands (NNN). The cod complexes have been prepared through deprotonation of their mononuclear amine precursors [(NHNN)RhI(cod)] in the presence of [RhI(cod)]+. Reaction of the binuclear complexes [(NNN)RhI 2(cod)2] with CO results in the complexes [(NNN)RhI 2(CO)4]. For NNN chelating imidazoleamidoimidazole ligand, the X-ray structures of [(NNN)RhI 2(cod)2], [(NNN)RhI 2(CO)4], and their mononuclear amine precursor [(NHNN)RhI(cod)] are reported. Electrochemical oxidation of the complexes is related to the relative donor strength of the N-ligands.