Synthesis and characterization of polypyridineruthenium(II) complexes containing a linear ambidentate ligand, NCO− or NCS−, and reaction of isocyanato complexes under acidic conditions

Isocyanato and isothiocyanatopolypyridineruthenium complexes, [Ru(NCX)Y(bpy)(py)2]n+ (bpy=2,2′-bipyridine, py=pyridine; X=O, Y=NO2 for n=0, and Y=py for n=1; X=S, Y=NO2 for n=0, Y=NO for n=2, and Y=py for n=1), were synthesized by the reaction of polypyridineruthenium complexes with potassium cyanate or sodium thiocyanate salt. Isocyanatoruthenium(II) complexes, [Ru(NCO)(NO2)(bpy)(py)2] and [Ru(NCO)(bpy)(py)3]+, react under acidic conditions to form the corresponding ammineruthenium complexes, [Ru(NO)(NH3)(bpy)(py)2]3+. The molecular structures of [Ru(NCO)(bpy)(py)3]ClO4, [Ru(NCS)(NO)(bpy)(py)2](PF6)2 and [Ru(NO)(NH3)(bpy)(py)2](PF6)3 were determined by X-ray crystallography.