Cation Effect on Formation of Preyssler-type 30-Tungsto-5-phosphate: Enhanced Yield of Na-encapsulated Derivative and Direct Synthesis of Ca- and Bi-Encapsulated Derivatives
Cation Effect on Formation of Preyssler-type 30-Tungsto-5-phosphate: Enhanced Yield of Na-encapsulated Derivative and Direct Synthesis of Ca- and Bi-Encapsulated Derivatives
复制标题
阳离子对形成 Preyssler 型 30-桐甾-5-磷酸的影响： 提高 Na-包封衍生物的产量以及直接合成 Ca-和 Bi- 包封衍生物
DOI：
10.1002/zaac.201500679
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发表时间：
2015-12-01
影响因子：
1.4
通讯作者：
Sadakane, Masahiro
中科院分区：
文献类型：
--
作者：
Hayashi, Akio;Haioka, Terufumi;Sadakane, Masahiro
研究了反应体系中阳离子对Preyssler-Jeannin-Pope型30-钨-5-磷酸盐[P5 W30 O 110 Na]（14-）合成的影响。磷钨比约为1：1的磷酸盐和钨酸盐的反应。3.9在无阳离子的酸性水溶液中选择性地生成Dawson型18-钨-2-磷酸盐[P2 W18 O 62]（6-）。在所有的碱金属阳离子中，只有Na+允许形成Preyssler型聚阴离子[P5 W30 O 110 Na]（14-），其具有包封的Na+离子，并且可以通过增加Na+量来提高产物产率。Li+离子的存在反而导致Dawson型聚阴离子[P2 W18 O 62] 6-，而K+、Rb+和Cs+选择性地导致Keggin型聚阴离子[PW 12 O 40]（3-）。本文提出了一种改进的钠包封Preyssler离子的合成方法，从而提高了分离产率。此外，Ca ~（2+）和Bi ~（3+）化合物的加入，可分别形成Ca ~（2+）和Bi ~（3+）包裹的Preyssler型聚阴离子[P_5W_30O_110Ca]（13-）和[P_5W_30O_110Bi]（12-）。此外，首次报道了Bi ~（3+）包覆的Preyssler型聚阴离子[P_5W_30O_110Bi]（12-）的单晶XRD结构。
The effect of cations in a reaction mixture for the preparation of the Preyssler-Jeannin-Pope type 30-tungsto-5-phosphate [P5W30O110Na](14-) is investigated. Reaction of phosphate and tungstate with a P/W ratio of ca. 3.9 in an acidic aqueous solution without cations selectively leads to the Dawson-type 18-tungsto-2-phosphate, [P2W18O62](6-). Amongst all the alkali cations, only Na+ allows formation of the Preyssler-type polyanion [P5W30O110Na](14-), with an encapsulated Na+ ion, and the product yield can be improved by increasing Na+ amount. The presence of Li+ ions instead results in the Dawson-type polyanion [P2W18O62] 6-, whereas K+, Rb+, and Cs+ selectively result in the Keggin-type polyanion [PW12O40](3-). An improved synthetic procedure for the Na+-encapsulated Preyssler-ion leading to a higher isolated yield is presented. Furthermore, addition of Ca2+ and Bi3+ compounds allows formation of the Ca2+- and Bi3+-encapsulated Preyssler-type polyanions, [P5W30O110Ca](13-) and [P5W30O110Bi](12-), respectively. Furthermore, single-crystal XRD structure of the Bi3+ encapsulated Preyssler-type polyanions, [P5W30O110Bi](12-), is presented for the first time.