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Neue Chalkogenolatkomplexe : Synthesen sowie strukturelle und spektroskopische Untersuchungen

Lackmann, Jörg

New chalcogenolate-complexes Syntheses as well as structural and spectroscopical researches This dissertation examines reactions that lead to the synthese of new chalcogenolate complexes. 2-propanchalkogenolat was used as ligand system, that particularly fits into this system. The reaction of this ligands with metalsalts demonstrate some types of homometallic complexes [M2(EiPr)6]2- (M = Mn, Fe, Zn; E = S, Se) that were used as precursors. The bi-nuclear chalcogenolate complexes were used in further reactions by transposing other metal species as precursor. The fact of the matter is that new ways of synthese should show a determined synthesis of heterometallic complexes. It was possible to synthetize and characterize heterometallic chalcogenolate complex-anions [Zn3Cu(SiPr)6Cl3]2-, [Zn4Cu4(SiPr)12S]2-, [Zn4Cu4(SeiPr)12Se]2- and [Zn5Cu3(SeiPr)12Se]- with the aid of the developed strategies of synthese. The synthesis of the complex-anion [Mn2Mo(SiPr)8]- shows that the same strategy of synthese, which was actually used to connect metals coordinated in tetrahedral manner with trigonal-planar coordinated CuSR3-fragments, can also be used to connect coordination-polyeder of other geometry. The tetrahedral Mn(SiPr)4-sub-units are over opposite-lying squares of Mo(SiPr)6-octahedron connected to a linear tri-nuclear complex-anion. This complex-anion is the first homoleptic thiolate-complex, which contains molybdän in the oxidation-state +3. This systematical research and synthesis or the integration of complexes ,respectively, of this work and further literature describing complexes lead primarily to a composition of a superior principle that can be put with multi-nuclear heterometallic-chalcogenolate complex in one similiar structural context. This principle is able to ordinate all cubelike complexes with M8µ-ER12-framework: one central chalcogenide- or halogenide-core is surrounded by a M8-metal-cage, which is more or less pulled cubical. This cage is enclosed by an exterior icosahedral or cuboctahedral µ-SR12-polyhedron.

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Lackmann, Jörg: Neue Chalkogenolatkomplexe. Synthesen sowie strukturelle und spektroskopische Untersuchungen.


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