Treatment of perchlorobuta-1,3-diene with 4-(N,N-dimethylamino)pyridine resulted in the formation of 1,1¢,1¢¢,1¢¢¢-(2,3-dichlorobuta-1,3-diene-1,1,4,4-tetrayl)tetrakis[4-(dimethylamino)pyridinium] tetrachloride (structure confirmed by X-ray analysis), which was converted into persulfurated butatrienes ([3]cumulenes), pentakis(sulfanyl)-substituted buta-1,3-dienes, or tetrakis(sulfanyl)-substituted 2,3-dichlorobuta-1,3-dienes by reactions with thiolates or a sulfinate. The outcome of the reaction depends on the reaction conditions and the substitution pattern of the starting sulfur nucleophiles.