Reaction of cis-Ru(bpy)(2)Cl-2 with 1,2-benzenedithiol afforded a monosulfhydryl-monosulfinate complex, [Ru(bpy)(2)(S center dot SO2)] (1). Complex 1 readily undergoes oxidation when treated with 30% H2O2 and also upon exposure to atmospheric O-2 (rapidly in bright light) to afford the disulfinate complex, [Ru(bpy)(2)(SO2 center dot SO2)] (2). Complexes 1 and 2 were studied using various analytical techniques including elemental analysis, UV-vis, mass spectroscopy, NMR, IR spectroscopy, cyclic voltammetry, X-ray crystallography (for 2). Density functional theory computation was employed with extended charge decomposition and natural population analyses. The agreement between the observed electronic spectrum and that predicted by time dependent DFT, and between the observed infrared spectrum and that predicted by DFT, is truly exceptional. These molecules are relevant to the very unusual active site in the metalloenzyme nitrile hydratase.