Hennig Christoph, Weiss Stephan, Kraus Werner, Kretzschmar Jerome, Scheinost Andreas C
Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology , Bautzner Landstrasse 400, 01328 Dresden, Germany.
The Rossendorf Beamline at ESRF , BP 220, 38043 Grenoble, France.
Inorg Chem. 2017 Mar 6;56(5):2473-2480. doi: 10.1021/acs.inorgchem.6b01624. Epub 2017 Feb 15.
Complex formation and the coordination of zirconium with acetic acid were investigated with Zr K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) and single-crystal diffraction. Zr K-edge EXAFS spectra show that a stepwise increase of acetic acid in aqueous solution with 0.1 M Zr(IV) leads to a structural rearrangement from initial tetranuclear hydrolysis species [Zr(OH)(OH)] to a hexanuclear acetate species Zr(O)(OH)(CHCOO). The solution species Zr(O)(OH)(CHCOO) was preserved in crystals by slow evaporation of the aqueous solution. Single-crystal diffraction reveals an uncharged hexanuclear cluster in solid Zr(μ-O)(μ-OH)(CHCOO)·8.5HO. EXAFS measurements show that the structures of the hexanuclear zirconium acetate cluster in solution and the solid state are identical.
利用Zr K边扩展X射线吸收精细结构光谱（EXAFS）和单晶衍射研究了锆与乙酸的配合物形成及配位情况。Zr K边EXAFS光谱表明，在含有0.1 M Zr(IV)的水溶液中逐步增加乙酸会导致结构从最初的四核水解物种[Zr(OH)(OH)]重排为六核乙酸盐物种Zr(O)(OH)(CHCOO)。通过水溶液的缓慢蒸发，溶液物种Zr(O)(OH)(CHCOO)在晶体中得以保留。单晶衍射揭示了固体Zr(μ-O)(μ-OH)(CHCOO)·8.5HO中存在一个不带电荷的六核簇。EXAFS测量表明，溶液和固态中的六核乙酸锆簇结构相同。
