Schwefel‐Anionen mit der Koordinationszahl 3: Synthese, Struktur und Existenzbereich

Abstract

Die Umsetzungen von Sulfonylschwefeldiimiden rnit Alkalialkoholaten fuhren zu den Salzen l a -g. Eine Rontgenstrukturanalyse von I f zeigt die erwartete Geometrie rnit dem zentralen dreifach koordinierten Schwefelatom. l c reagiert rnit elementarem Chlor zum Natriumsalz 2 der azaanalogen Chlorsulfonsaure. Setzt man NaNH, als Nucleophil rnit Bis(phenylsulfony1)schwefeldiimid um, so entsteht als Hauptprodukt Tris(phenylsulfony1imido)sulfit (3), dessen Struktur ebenfalls durch eine Rontgenstrukturanalyse aufgeklart wurde. Analog dem SO:--Anion besitzt in 3 das zentrale Schwefelatom trigonal pyramidale Konfiguration. Die azaanaloge Verbindung 4 der Fluorsulfinsaure entsteht bei der Reaktion von Bis(phenylsulfony1)schwefeldiimid mit sorgfaltig getrocknetem CsF. Bei der Umsetzung von Bis(trimethylsi1yl)schwefeldiimid rnit CsF, das etwa 7% Wasser enthalt, bildet sich das monomere Caesiumsalz des Sulfimids, das nach Kationenaustausch in Form der Salze 5a und b charakterisiert wurde. Tetraphenylphosphoniummethoxid reagiert rnit 5-(Trimethylsilyloxy)-l ,3h4,2,4,6-dithiatriazin-1 ,1-dioxid (6) unter CH,OSi(CH,),-Abspaltung zu 7. Das Anion von 7 enthalt eine Carbonylgruppe. Anions of Sulfur with the Coordination Number 3: Synthesis, Structure, and Range of ExistenceSulfonylsulfur diimides react with alkali alcoxides to form the salts l a -g . An X-ray structural analysis of I f shows the expected geometry with the central threefold coordinated sulfur atom. l c reacts with elemental chlorine to yield the sodium salt 2, the aza analogue of chlorosulfonic acid. When NaNH, is used as a nucleophile for the reaction with bis(phenylsulfony1)sulfur diimide, tris(phenylsulfony1imido)sulfite (3) is formed as the main product. Also the structure of 3 was elucidated by means of an X-ray analysis. Analogous to the SO:--anion, 3 has a central sulfur atom with trigonal pyramidal configuration. The analogous aza compound of the fluorosulfinic acid 4 is formed by the reaction of bis(phenylsulfony1)sulfur diimide with carefully dried CsF. By the reaction of bis(trimethylsily1)sulfur diimide with CsF, which contains about 7% of water, the monomeric cesium salt of sulfonimide is formed. The salts 5a und b were obtained by cation exchange of the cesium salt. Tetraphenylphosphonium methoxide reacts with 5-(trimethylsilyloxy)-1 ,3h4,2,4,6-dithiatriazin 1 ,I-dioxide (6) by elimination of CH,OSi(CH,), to yield 7. The anion of 7 contains one carbonyl group.Kationen des Schwefels rnit der Koordinationszahl 3 werden in zahlreichen Publikationen' -, ) beschrieben. Entsprechende Anionen des Schwefels sind praktisch nur vom 0 Verlag

Coordination of Halide and Chalcogenolate Anions to Heavier 1,2,5-Chalcogenadiazoles: Experiment and Theory

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