The reactivity of N -thiophthalimides with silyl chalcogenides is described. Treatment of N -thiophthalimides with bis(trimethylsilyl) sulfide [(Me3 Si)2 S] leads to the formation of a mixture of the corresponding disulfides and trisulfides. On the other hand, N -thiophthalimides react with bis(trimethylsilyl) selenide [(Me3 Si)2 Se] under TBAF catalysis to smoothly give variously substituted diaryl, divinyl, and dialkyl disulfides; formation of a selenotrisulfide (dithiaselane, RSSeSR) is rationalized as an intermediate. Exploiting the different chemical behavior of silyl chalcogenides, we have disclosed a novel, selective, and operationally simple method to access disulfides in good yields under mild conditions. [ABSTRACT FROM AUTHOR]