Oxoanionic noble metal compounds from fuming nitric acid: the palladium examples Pd(NO3)2 and Pd(CH3SO3)2.
Oxoanionic noble metal compounds from fuming nitric acid: the palladium examples Pd(NO3)2 and Pd(CH3SO3)2.
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DOI：
10.1002/chem.201405355
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发表时间：
2015-01
期刊：
影响因子：
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通讯作者：
Jörn Bruns;T. Klüner;M. Wickleder
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文献类型：
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作者：
Jörn Bruns;T. Klüner;M. Wickleder
元素钯在发烟硝酸和吡啶-SO 3络合物的混合物中于100 °C氧化，得到无水硝酸盐Pd（NO3）2（单斜晶系，P2（1）/n，Z=2，a=469.12（3）pm，B=593.89（3）pm，c=805.72（4）pm，β=105.989（3）°，V=215.79（2）μ m（3））。Pd（2+）离子与四个单齿硝酸根基团形成正方形平面配位，这些硝酸根基团与另外的钯原子连接，从而形成层状结构。元素钯与发烟硝酸和甲磺酸的混合物在120 °C下反应，得到Pd（CH 3SO 3）2的单晶（单斜晶系，P2（1）/n，Z=2，a=480.44（1）pm，B=1085.53（3）pm，c=739.78（2）pm，β=102.785（1）°，V=376.254（17）μ m（3））。同样在这种结构中，Pd（2+）离子与四个单齿阴离子处于正方形平面配位;然而，与相邻钯原子的连接导致链状结构。用DSC/TG研究了化合物的热分解过程。此外，红外光谱和拉曼光谱已被记录，并进行了分配的基础上的理论研究所观察到的振动频率。
The oxidation of elemental palladium at 100 °C in a mixture of fuming nitric acid and a pyridine-SO3 complex leads to the anhydrous nitrate Pd(NO3)2 (monoclinic, P2(1)/n, Z=2, a=469.12(3) pm, b=593.89(3) pm, c=805.72(4) pm, β=105.989(3)°, V=215.79(2) Å(3)). The Pd(2+) ions are in square-planar coordination with four monodentate nitrate groups which are connected to further palladium atoms, leading to a layer structure. The reaction of elemental palladium with a mixture of fuming nitric acid and methanesulfonic acid at 120 °C leads to single crystals of Pd(CH3SO3)2 (monoclinic, P2(1)/n, Z=2, a=480.44(1) pm, b=1085.53(3) pm, c=739.78(2) pm, β=102.785(1)°, V=376.254(17) Å(3)). Also in this structure the Pd(2+) ions are in square-planar coordination with four monodentate anions; however, the connection to adjacent palladium atoms leads to a chain-type structure. The thermal decomposition of the compounds has been investigated by means of DSC/TG measurements. Furthermore, IR and Raman spectra have been recorded, and an assignment of the observed vibrational frequencies has been carried out based on theoretical investigations.