Korenev Vladimir S, Abramov Pavel A, Vicent Cristian, Zhdanov Artem A, Tsygankova Alphiya R, Sokolov Maxim N, Fedin Vladimir P
Nikolaev Institute of Inorganic Chemistry SB RAS, Prospect Lavrentyeva 3, 630090 Novosibirsk, Russia.
Dalton Trans. 2015 May 21;44(19):8839-45. doi: 10.1039/c5dt00349k.
The synthesis and characterization of three novel keplerate-type compounds containing the {W72Mo60} mixed-metal core are reported. Complexes (NH4)72[{W6O21(H2O)6}12{Mo2O4(SeO4)}30]·150H2O·6(NH4)2SeO4 (1a) and (NH4)25(NH2Me2)47[{W6O21(H2O)6}12{Mo2O4(SeO4)}30]·130H2O·3(NH4)2SeO4 (1b) were prepared by ligand substitution from the acetate anionic complex {W6O21(H2O)5(CH3COO)0.5}12{Mo2O4(CH3COO)}30 and selenate. The selenate anions in keplerate ions {W6O21(H2O)6}12{Mo2O4(SeO4)}30 are very labile and easily aquate with the formation of {W6O21(H2O)6}12{Mo2O4}30(SeO4)20(H2O)20, which was isolated as (NH4)20(NH2Me2)32[{W6O21(H2O)6}12{Mo2O4}30(SeO4)20(H2O)20]·150H2O (2) and structurally characterized. In the crystal structure of 2 selenate has several coordination modes, preferentially bonding to the {Mo2O4}(2+) units, and, additionally, to the {(W)W5} pentagonal blocks. The compounds have been characterized by elemental analysis, Raman, IR and (77)Se NMR spectroscopy, and by ESI mass spectrometry. Capillary electrophoresis was used for characterization of keplerates in solution for the first time.
报道了三种含{W72Mo60}混合金属核的新型开普勒型化合物的合成与表征。配合物(NH4)72[{W6O21(H2O)6}12{Mo2O4(SeO4)}30]·150H2O·6(NH4)2SeO4 (1a)和(NH4)25(NH2Me2)47[{W6O21(H2O)6}12{Mo2O4(SeO4)}30]·130H2O·3(NH4)2SeO4 (1b)是通过从醋酸根阴离子配合物{W6O21(H2O)5(CH3COO)0.5}12{Mo2O4(CH3COO)}30和硒酸盐进行配体取代制备的。开普勒离子{W6O21(H2O)6}12{Mo2O4(SeO4)}30中的硒酸根阴离子非常不稳定，容易水合形成{W6O21(H2O)6}12{Mo2O4}30(SeO4)20(H2O)20，其被分离为(NH4)20(NH2Me2)32[{W6O21(H2O)6}12{Mo2O4}30(SeO4)20(H2O)20]·150H2O (2)并进行了结构表征。在2的晶体结构中，硒酸盐有几种配位模式，优先与{Mo2O4}(2+)单元结合，此外还与{(W)W5}五角形块结合。这些化合物通过元素分析、拉曼光谱、红外光谱和(77)Se核磁共振光谱以及电喷雾质谱进行了表征。首次使用毛细管电泳对溶液中的开普勒化合物进行表征。
