Synthese, Strukturen und Eigenschaften der Cyclothiaselenazenium‐Kationen [Se 2 N 2 S] 2 2+ , [XSe 2 N 2 S] + , [Se 2 N 2 S] 2+ , [S 3 SeN 5 ] + sowie Cl 2 Se 2 N 2 S und SeSN 2 ṁ TiCl 4

Synthesis, Structures, and Properties of Cyclothiaselenazenium Cations [[Se2N2S]22+, [XSe2N2S]+, [Se2N2S]2+, [S3SeN5]+as well as Cl2Se2N2S and SeSN2 and SeSN2 ṁ TiCl4 Bis(sulfinylamino)selane (1), prepared from Se2Cl2 and (CH3)3SiNSO, reacts with Lewis acids such as MF5 (M = As, Sb, Nb) and BF3 to form bis(1,3,4,2,5-thiadiselenadiazolium) cations (3) with counter anions AsF-6 (3a), SbF-6 (3b), NbF-6 (3c), BF-4 (3d). Treatment of Se2Cl2 with LiN[Si(CH3)3]2 leads to [(CH3)3Si]2NSexN[Si(CH3)3]2 (x = 1, 2a: 2, 2b). From 2a and 2a and SeCl4 explosive Se4N4 is obtained. Chlorination of 3a and 3c gives [ClSe2N2S]+[MF6]- (M = As, 4a, and Nb, 4c). Analogous bromination of 3a provides [BrSe2N2S]+ [AsF6]- (4b). This type of chlorinated five-membered rings is also obtained directly from 1 and SbCl5 and PCl5 or SeCl4. The products isolated are [ClSe2N2S]+ [SbCl6]- (4d) and [ClSe2N2S]+Cl- (4e). – A covalent species 5, isomeric to 4e, is obtained from 1 and POCl3, and a four-membered ring SeSN2 ṁ TiCl4 (6) from 1 and TiCl4. When 3a or 1 is treated with a two- or threefold excess of AsF5 the stable dication [Se2N2S]2+ (7) is formed. It arises also from 4e and AgAsF6. Attempts to replace TiCl4 in 6 by AsF5 lead to [SeS3N5]+ [AsF6]- (8) with a bicyclic structure for the cation. X-ray structure analyses for 1, 4c, 4d, 4e, 5, and 8 are performed.