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Titel:Contributions to siloxane coordination chemistry and silicon based crown-ether analogues via s-block metal templated Si-O bond activation
Autor:Dankert, Fabian
Weitere Beteiligte: von Hänisch, Carsten (Prof. Dr.)
URN: urn:nbn:de:hebis:04-z2021-00453
DDC:540 Chemie
Titel (trans.):Beiträge zur Siloxankoordinationschemie und siliziumbasierte Kronenether mittels s-Block Metall templatgesteuerter Si-O Bindungsaktivierung


Koordinationschemie, Crown Ethers, Kronenether, Silizium, Coordination Chemistry, Templates, Siloxane, Wirt-Gast Chemie, Silicon, Host-Guest Chemistry, Siloxanes, Template, Bond Activation, Bindungsaktivierung

Silicone and Siloxane derivatives (e.g. (Me2SiO)n) are known to be chemically inert and hydrophobic materials. To bind cations thus requires sophisticated techniques to activate Si-O bonds for coordination. Central part of this thesis is therefor establishing Lewis acidic systems which allow effective Si-O bond activation. In addition, establishing suitable templates allow obtaining cation specific compounds in ring-opening oligomerization reactions. These reactions enable the synthesis of crown-ether analogues which formally resemble “inorganic” architectures of crown-ethers. So far, these ligands could not be synthesized by other means. Inorganic crown-ethers might show a reduced capability of binding cations but are remarkably stable in solution as long as a suitable metal ion is present which can act as a template. It could be shown that nine- and twelve membered cycles coordinate the cations Li+, Na+, Ca2+, Sr2+ and even H+ selectively. Hence, inorganic crown-ether analogues show an ion-selectivity towards chemically hard cations which has not been observed for their organic counterparts. In addition, templated synthesis has not yet been observed for conventional crown-ether analogues which is why a novel reactivity pattern is also presented here. The thesis does not only provide the synthesis of coordination compounds of inorganic crown-ether analogues but also that of related systems such as coordination compounds of hybrid disila-crown-ethers and cyclosiloxanes.

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