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978-3-8439-2108-4, Reihe Anorganische Chemie
Neue Komplexe des einwertigen Quecksilbers mit schwach koordinierenden Anionen und verwandte Verbindungen
353 Seiten, Dissertation Universität Köln (2014), Softcover, A5
In this work, nine new crystal structures of complexes of monovalent mercury with crown ether ligands and different weakly coordinating anions as well as two crystal structures of previously unknown Hg(I) salts are presented. Another Hg(I) salt and another Hg(I) crown ether complex compound could be detected by vibrational spectroscopy. Furthermore, the crystal structures of six crown ether complexes with various cations and the boranate anions (B12Cl12)2- and (B12I12)2- are presented.
In the structural analysis of the Hg(I) crown ether compounds factors are revealed that can affect the stability of Hg(I) complexes. This analysis is done on the basis of the crystal structures of the compounds presented in this work and other compounds known from the literature.
With the results of quantum mechanical calculations the electronic structure of some of Hg(I) crown ether complexes is under investigation. Furthermore, the structures of some experimentally undetectable Cd(I) and Zn(I) crown ether complex compounds were optimized by quantum mechanical calculations. In the analysis of the electronic structure these complexes are compared with analogous Hg(I) compounds. Using the results of quantum mechanical calculations, the influence of the ligands on the stability of the complexes is investigated. It can be shown that the tested monovalent zinc and cadmium crown ether complexes tend to disproportionate.