The brominated sulfimide Ph₂SNBr reacts with diphosphines 1,2-(PPh₂)₂C₂H₄ and 1,4-(Ph₂P)₂(C₆H₄) to give the bis-N-phosphoniosulfimidium cations [1,2-(Ph₂PNSPh₂)₂C₂H₄]²⁺ and [1,4-(Ph₂PNSPh₂)₂(C₆H₄)]²⁺, respectively. Treatment of the bis-sulfimide 1,4-[PhSNH]₂C₆H₄ with N-bromosuccinimide results in 1,4-[PhSNBr]₂C₆H₄, which in turn reacts with triphenylphosphine to generate [1,4-(PhS{NSPPh₃})₂C₆H₄]Br₂. Both Ph₂SNBr and 1,4-[PhSNBr]₂C₆H₄ react with the thio-ether crown [9-ane]S₃, giving [9[ane]S₃NSPh₂]Br and [1,4-{[9-ane]S₂S(NSPh)₂C₆H₄]Br₂, respectively. The first examples of seleniosulfimidium salts have been isolated from the reactions of Ph₂SNBr and 1,4(PhS{NBr})₂C₆H₄ with Ph₂Se and the structures of the [Ph₂SNSePh₂]⁺ and [1,4-(PhSNSePh₂)₂C₆H₄]²⁺ cations confirmed by X-ray crystallography. Reaction of 1,2-PhS(NH)C₆H₄SPh with one equivalent of N-bromosuccinimide followed by addition of Na[BPh₄] results in [1,2-(PhS)₂(μ-N)C₆H₄][BPh₄] in which a CCSNS ring is observed; two forms of this material may be isolated upon crystallisation—X-ray crystallography reveals them to differ by the relative orientations of the phenyl rings.