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. (C) 2001 Elsevier Science B.V. All rights reserved.