Synthesis and characterization of trans-[Ru(NO)Cl(L)4](PF6)2 (L = isonicotinamide; 4-acetylpyridine) and related species

The trans-[RuCl2(L)4], trans-[Ru(NO)Cl (L)4](PF6)2 (L = isonicotinamide and 4-acetylpyridine) and trans-[Ru(NO)(OH)(py)4]Cl2 (py = pyridine) complexes have been prepared and characterized by elemental analysis, UV–visible, infrared, and 1H NMR spectroscopies, and cyclic voltammetry. The MLCT band energies of trans-[RuCl2(L)4] increase in the order 4-acpy < isn < py. The reduction potentials of trans-[RuCl2(L)4] and trans-[Ru(NO)Cl(L)4]2+ increase in the order py < isn < 4-acpy. The stretching band frequency, νNO, of the nitrosyl complexes ranges from 1913 to 1852 cm−1 indicating a nitrosonium character for the NO ligand. Due to the large π-acceptor ability of the equatorial ligands, the coordinated water is much more acidic in the water soluble trans-[Ru(NO)(H2O)(py)4]3+ than in trans-[Ru(NO)(H2O)(NH3)4]3+.

The syntheses and characterization of trans-[RuCl2(L)4], trans-[RuCl(NO)(L)4](PF6)2 (L = isonicotoninamide; 4-acetylpýridine) and the water soluble trans-[Ru(OH)(NO)(pyridine)4]Cl2 are described. All nitrosyl complexes show the infrared νNO band consistent with a nitrosonium character of the NO ligand and undergo successive reductions, passing from {RuNO}6 to {RuNO}7 to {RuNO}8 in acetonitrile.Figure optionsDownload as PowerPoint slide