Über metallreiche Halogenide und Chalkogenide früher Übergangsmetalle
This habilitation thesis describes the syntheses and characterizations of mostly new metal-rich cluster compounds of early transition elements. It is devided into 4 parts. <br> <br> The first part describes the syntheses and solid-state X-ray structures of a total of 14 mixed-halide (iodide-chloride) zirconium cluster phases, which crystallize in 9 different (some novel) structure types. All these cluster phases contain octahedral Zr6Z-units that are centered by an interstitial atom Z. Phase widths and relations between the differend structure types are discussed. <br> <br> The second part deals with molecular (soluble) zirconium cluster phases which are excised from solid-state precursors. It is shown that liquid mixtures of 1,3-dialkylimidazolium bromide and AlBr3 as well as molten 18-crown-6 are useful solvents for molecular zirconium cluster compounds. The syntheses and single crystal X-ray structures of 3 new materials are detailed. Furthermore, from the reaction of an iron containing Zr-cluster phase with KSCN crystals have been obtained from which a single crystal X-ray structure analysis shows that they contain a high symmetry Fe-cubane cluster.<br> <br> The third part of this thesis is concerned with theoretical investigations (Extended-Hckel band structure calculations) of a series of monoclinic phases which contain double-octahedral chains of rare earth metal clusters of the general formula RE3I3Z (RE = rare-earth metal atoms). The results of the electronic band structure calculations show that the observed structural variations within this series depend largely on the difference of the orbital energies of the rare earth metals and the interstitials. <br> <br> In the last part the phase pure synthesis of Nb21S8 and measurements of physical properties (electrical conductivity and magnetical susceptibility) as well as results from electronic band structure calculations (LMTO) are described. The property measurements show that this metal rich sulfide becomes superconducting below 3.7(2) K. The results from the electronic band structure calculations indicate the existence of an arrangement of electronic levels ("fingerprint") which favors the formation of superconducting Cooper pairs.