Synthese, Strukturen und Eigenschaften der Cyclothiaselenazenium‐Kationen [Se2N2S]22+, [XSe2N2S]+, [Se2N2S]2+, [S3SeN5]+ sowie Cl2Se2N2S und SeSN2 ṁ TiCl4

Abstract

Synthesis, Structures, and Properties of Cyclothiaselenazenium Cations [[Se2N2S]22+, [XSe2N2S]+, [Se2N2S]2+, [S3SeN5]+as well as Cl2Se2N2S and SeSN2 and SeSN2 ṁ TiCl4Bis(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.