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Hopfinger, Mathias (2012): Protonierte Schwefelsäuren. Dissertation, LMU München: Faculty of Chemistry and Pharmacy



Most of the disulfuric acids like thiosulfuric acid (H2S2O3), dithionous acid (H2S2O4), disulfurous acid, (H2S2O5), dithionic acid (H2S2O6), disulfuric acid (H2S2O7) and peroxydisulfuric acid (H2S2O8) have never been obtained as pure compounds, because they are not stable at ambient temperatures. Therefore no experimental evidences are known for their structures. In this thesis, the synthesis and spectroscopical characterization of the disulfuric acids H2S2Ox (x = 3,4,6,8) is presented. The compounds were obtained by the reaction of dry Na2S2Ox or K2S2Ox with anhydrous HF at −60 °C. The protonated species H3S2Oy+MF6− (y = 3 - 8) were synthesized and characterized using the superacidic systems HF/MF5 (M = As, Sb). The protonation of sulfuric acid, (H3SO4+)n(GeF5−)n, with the new superacidic system HF/GeF4 is presented and gives evidence for the acid strength of this system. Moreover, the first single crystal structure of protonated dimethylsulfoxide (DMSO), [(CH3)2SOH+]4[Ge3F16]4− is discussed. The protonated forms of the aminosulfonic acids NH3SO3, NH3CH2SO3, NH3C2H4SO3 and methanesulfonamide (CH3SO2NH2) are described. In this context, the first crystal structure of protonated taurine, NH3C2H4SO3H+SbF6− is discussed.