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]22⊕(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.