Herstellung und Charakterisierung der «Cyclothiadi(selenazenium)»-Kationen [Se2N2S]22⊕, [XSe2N2S]⊕ und [Se2N2S]2⊕

Abstract

Bis(sulfinylamido)selenium, prepared from Se₂Cl₂ and (CH₃)₃SiNSO, forms with MF₅ (molar ratio 1:1) in SO₂ salts of the dimeric so-called cyclothiadi(selenazenium) cation  [Se₂N₂S]₂^2⊕(MF₆^⊖)₂ (1a: M = As; 1b: M = Sb; 1c: M = Nb). When the compounds 1a and 1c are treated with Cl₂ or 1a with Br₂ the corresponding halogenocyclothiadi(selenazenium) derivatives [XSe₂N₂S]^⊕MF₆^⊖ (2a: M = As, X = Cl; 2b: M = As, X = Br; 3a: M = Nb, X = Cl) are obtained. – Similarly Se(NSO)₂ reacts with SbCl₅ (molar ratio 1:0.5-0.7) in CH₂Cl₂ to yield [ClSe₂N₂S]^⊕SbCl₆^⊖ (3b). With PCl₅ in CH₂Cl₂ solution Se(NSO)₂ reacts to [ClSe₂N₂S]^⊕Cl^⊖ (3c) which provides in a metathetical reaction with AgAsF₆ almost quantitatively [Se₂N₂S]^2⊕(AsF₆^⊖)₂ (4). The latter salt of a dication can also be made from Se(NSO)₂ and AsF₅ (molar ratio 1:3) in SO₂. Crystal structure analyses for 1a and 3a-c prove the suggested structures.