有机膦、胂、睇合钨钼聚多酸盐的研究——Ⅷ.3-硝基-4-羟基苯胂合钼聚多酸盐的制备和解聚法制备有机胂合钼聚多酸盐的尝试

为研究有机基团对有机胂合钼聚多酸盐类型的影响,试验了3-硝基-4-羟基苯胂酸与钼酸钠在pH为3～5条件下的反应。制得了两种新化合物:(1)(NH_4)_6(3-NO_2-4-OHC_6H_3As)_2Mo_6O_(25)](2)(CN_3H_6)_6(3-NO_2-4-OHC_6H_3As)_2Mo_6O_(25)]。报道和讨论了它们的红外、可见与紫外光谱、热分解性质和电化学氧化还原性质。它们与其钨同系物类型相同。化合物(1)可用酸化聚合法及解聚法制得,经过实验比较证实了以七钼酸铵为原料的解聚法具有产物纯化方便、得率高的优点。

STUDIES ON ORGANO-PHOSPHORUS,-ARSENIC AND -ANTIMONY POLYTUNGSTATES AND POLYMOLYBDATES VIII. PREPARATION AND PROPERTIES OF 3-NITRO -4-HYDROXYPHENYLARSENIC POLYMOLYBDATES AND DEGRADATION METHOD FOR PREPARING ORGANOARSENIC POLYMOLYBDATES

In order to investigate the effect of organic groups on the types of organoarsenic polymolybdates, the reaction of 3-nitro-4-hydroxyphenylarsonic acid with sodium molybdate has been tested at pH = 3-5. Two salts have been prepared and characterized: (1) (NH4)6(3-NO2-4-OHC6H3As)2Mo6O25] (2) (CN3H6)6(3-NO2-4-OHC6H3As)2-MO6O25]. The IR, UV spectra, thermal properties and electrochemical behaviors have been reported and discussed. They belong to the same type as that of their tungsten congener. Single-crystal X-ray diffraction studies show that (2) and its tungsten congener have not only the same space group, but also very close cell dimensions. Compound (1) has been prepared by two different method: acidification building up method and degradation method. It is verified that the degradation method starting with ammonium heptamolybdate has advantage in the simplification of reaction product, thus leading to its higher yield.