Syntheses and Characterization of Polyimidosulfate Complexes

Abstract

This thesis focuses on the tetrakis(tertbutyl)imidosulfate S(NtBu)4 2-and the corresponding protonated compound OS(NtBu)2(NHtBu).In the seventies Glemser and Wegener obtained the first sulfur-nitrogen compound with sulfur in the oxidation state of +VI. [28] S(NSiMe3)3 was synthesized in the reaction of sulfur nitride trifluoride and lithium bis(trimethylsilyl)amide (Scheme 1.2, (I)). As a side product, bis(N-trimethylsilylimido)sulfur difluoride could be isolated. [28] In addition, Glemser et al. reported the synthesis of S(NtBu)3 via addition of NSF3 (II). [29] Alternatively, Verbeek et al. utilized OSF4 instead of NSF3 for the reaction of a sulfate anion analog (III). [30] Scheme 1.2: Syntheses of sulfurtriimide. [28][29][30] However, the yields of these reactions were very low because the substances are highly reactive. Thus, a new synthesis was developed realizing the oxidation of sulfur +IV to sulfur +VI of the iminosulfindiamide by bromine or iodine. [22,31] The involvement of halides suggests a radical mechanism with the characterized dimeric product given by Scheme 1.3.