Reaction of dithiols with Ni(dppe)Cl-2 gave monomeric or dimeric dithiolato compounds depending on the nature of the dithiol. Toluene-dithiol (TDT) and 1,2-benzenedithiol (I,2-BDT) gave Ni(dppe)(TDT) (I) and Ni(dppe)(1,2-BDT) (2), respectively, whereas 1,3-benzenedithiol (1,3-BDT) gave [Ni(dppe)Cl](2)(1,3-BDT) (3). Single crystal X-ray diffraction studies of 2 showed a square planar nickel environment. Complexes 1 and 2 reacted rapidly and reversibly with SO2 to form 1 . SO2 and 2 . SO2, respectively. The reversibility of the SO2 reactions was established by a combination of UV-Vis and H-1 NMR spectroscopy.