Zweikernige Zinkkomplexe als Modellverbindungen für Hydrolasen
TL;DRAbstract
The present work deals with the assembly and the reactivity of dinuclear zinc complexes of preorganizing pyrazolate-based dicompartimental ligands as model complexes for hydrolases. A set of nine different bis(aminomethyl) pyrazole ligands was synthesized in order to permit a systematic correlation of structure and reactivity of the corresponding dizinc complexes.In case of bis(tetradentate) pyrazolate ligands with short side arms, dinuclear zinc complexes with long Zn-Zn distances and a H3O2 or a HOHOMe bridge are obtained whereas long side arms lead to short Zn-Zn distances and a hydroxide bridge. In case of coordinatively unsaturated bis(tridentate) systems highly reactive dizinc species are formed that rapidly fixate aerial carbon dioxide as carbonate. In order to understand the composition and reactivity of the complexes in solution, the solid state structures - characterized by XRD - were complemented by potentiometric titrations.The kinetic parameters of the hydrolysis of the ph
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The present work deals with the assembly and the reactivity of dinuclear zinc complexes of preorganizing pyrazolate-based dicompartimental ligands as model complexes for hydrolases. A set of nine different bis(aminomethyl) pyrazole ligands was synthesized in order to permit a systematic correlation of structure and reactivity of the corresponding dizinc complexes.In case of bis(tetradentate) pyrazolate ligands with short side arms, dinuclear zinc complexes with long Zn-Zn distances and a H3O2 or a HOHOMe bridge are obtained whereas long side arms lead to short Zn-Zn distances and a hydroxide bridge. In case of coordinatively unsaturated bis(tridentate) systems highly reactive dizinc species are formed that rapidly fixate aerial carbon dioxide as carbonate. In order to understand the composition and reactivity of the complexes in solution, the solid state structures - characterized by XRD - were complemented by potentiometric titrations.The kinetic parameters of the hydrolysis of the ph
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