We report the unprecedented formation of a benzo-fused 1,3,2-dithiazolylium [AsF₆⁻] salt by a one step, quantitative, cycloaddition of SNSAsF₆ with 1,4-benzoquinone. In contrast, the reaction of SNSSbF₆ with 1,4-naphthaquinone results in 2,7-dicarbonylnaphtha-1,3,2-dithiazolylium [SbF₆⁻]. Both were reduced to the corresponding 7π radicals.