Synthese und Funktionalisierung von Verbindungen mit binären, ternären und quaternären Chalkogenidometallat-Anionen in ionischen Flüssigkeiten

The results, which were obtained within the framework of this Ph.D. project, can be divided by subject into two different parts according to the working title: The synthesis of novel compounds containing chalcogenidometalate anions (1) and the functionalization of chalcogenidometalate anions (2). Ionic liquids (ILs) were chosen as reaction media for these investigations. (1) Through careful selection of additives (e.g. SbCl3) the incorporation of metal or semimetal atoms into the anion structures of the reaction products was observed. The syntheses of 12, 2a2 and 2b2 resulted in compounds containing either a [Ge2Sb2S7]6[GeS4] assembly (12) or a one-dimensional {[Sn10O4S20][Sb3S4]2} anion framework (22). The influence of IL cations was examined by means of reactions resulting in {(C4C1C1Im)2[Sn3S7]} (1a3), {(C4C1C2Im)2[Sn3S7]} (1b3), and {(C4C1C2Im)2[Sn4S9]} (23). Additionally, 1b3 can be transformed into 1a3 via rapid organic cation exchange. (C14C1Im)8[Hg8Te16] (4) and (C16C1Im)8[Hg8Te16] (5) are compounds, in which the nature of the ionic liquid cations plays a key role. These compounds contain the literature-known [Hg8Te16]8– phorphyrinoid anions. (2) The usage of (C4C1C1Im)Cl or (C4C4C1Im)Cl yielded (C4C4C1Im)4[Sn10O4S16(SMe)4] (15) and (C4C4C1Im)4[Sn10O4S16(SMe)4] 16. These compounds contain methylated OTS anions. When SnCl4 was added to the reaction media, the successful synthesis of compound (C4C1Im)4[Sn10O4S16(SH)4] (2) containing a protonated OTS anion was obtained. Finally, the reaction of K4[SnS4]·4H2O with (C4C1C4Im)Br resulted in the successful butylation of the OTS anion: (C4C1C4Im)4[Sn10O4S16(SBu)4] (1a). In contrast to other chalcogenidometalates shown in this work, this compound is soluble in organic solvents (e.g. acetonitrile). Further functionalization of chalcogenidometalates could be obtained by the synthesis of (C10C1Im)6[Hg6Te10(TeDec)2] (3). This compound exhibits a decylated [Hg6Te12]8‒ anion and a lamellar structure.