In the present thesis, new polysulfates and hydrogenpolysulfates of Rare Earth and transition metals are described. The work focuses on the synthesis under harsh conditions, like usage of SO3 and trifluormethanesulfonic acid as both reactant and solvents. Another aspect is the structural determination by X-ray crystallography. Reactions in pure SO3 under the presence of the strong oxidizing agent XeF2 lead to new polysulfates and hydrogenpolysulfates. On the one hand the new disulfates K[Mn(S2O7)2] and Cs[Mn(S2O7)2] * SO3 could be obtained by the disproportion of hexafluoromanganates. Special about the cesium compound is the addition of sulfur trioxide molecules into the crystal structure. This can be seen as a frozen intermediate on the route towards higher polysulfates. On the other hand, KPr(S2O7)(S3O10) could be obtained, in which the Rare Earth cation could be stabilized by trisulfate anions for the first time ever seen. Furthermore, Ba(HS3O10)2 was synthesized, showing a coordination of the divalent alkaline metal center by hydrogentrisulfates. In comparison with other already known hydrogentrisulfates like M(HS3O10) with M = Na, K, Rb it can be seen, that the anions of Ba(HS3O10)2 and Na(HS3O10) built dimers, whereas K(HS3O10) and Rb(HS3O10) forming anionic chains. Reactions of Rare Earth oxides with trifluormethanesulfonic acid, trifluormethanesulfonic anhydrate and fuming nitric acid lead in the case of the heavier Rare Earth metals to the compounds RE(CF3SO3)3(H2O) with RE = Er, Tm and Lu and in the case of the lighter Rare Earth metals to (NO)5[RE(CF3SO3)8] with RE = La, Pr, Sm, Tb, Dy. The latter show an elusive coordination of triflate ligands towards the Rare Earth cation.Two Rare Earth sulfonates (Eu2(NH2BDS)3(NMP)8 and Eu(BTS)(DMA)5) could be synthesized by the reaction of EuCO3 with the respective sulfonic acids (anilinedisulfonic acid and benzenetrisulfonic acid) in organic solvents. Both compounds show a linkage of the europium atoms via sulfonic linkers.Last but not least the europium cluster {[Eu6O2]Eu2(OH)6}Cl12(Py)12 * 11 Py could be obtained by the reaction of EuOCl and LiH in pyridine. It consists of two [Eu4O]-tetrahedra, which can be seen as an excision of the EuOCl structure.
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