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A soluble phosphorus-centered keggin polyoxoniobate with bicapping vanadyl groups

机译:带有二帽化钒基的可溶的以磷为中心的乞金多羟基异戊酸酯

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摘要

A water-soluble tetramethyl- ammonium (TMA) salt of a novel Keggin-type polyoxoniobate has been isolated as TMA9[PV_2Nb_(12)O _(42)].19H_2O (1). This species contains a central phosphorus site and two capping vana- dyl sites. Previously only a single example of a phosphorus-containing poly- oxoniobate, [(PO_2)_3PNb _9O_(34)]~(15-), was known, which is a lacunary Keggin ion decorated with three PO2 units. However, that cluster was isolated as an insoluble structure consisting of chains linked by sodium counterions. In contrast, the [PV_2Nb_(12)O_(42)]9 cluster in 1 is stable over a wide pH range, as evident by 31P and 51V NMR, UV/Vis spectroscopy, and ESI-MS spectrometry. The ease of substitution of phosphate into the central tetrahedral position suggests that other oxoanions can be similarly substituted, promising a richer set of structures in this class.
机译:新型Keggin型聚氧杂铌酸盐的水溶性四甲基铵(TMA)盐已分离为TMA9 [PV_2Nb_(12)O _(42)]。19H_2O(1)。该物种包含一个中央磷位点和两个加帽钒位点。以前,仅知道一个含磷的聚氧杂铌酸盐的单个实例,[(PO_2)_3PNb _9O_(34)]〜(15-),这是一个用三个PO2单元修饰的腔Keggin离子。然而,该簇被分离为不溶性结构,其由通过钠抗衡离子连接的链组成。相比之下,[PV_2Nb_(12)O_(42)] 9团簇1在很宽的pH范围内是稳定的,如31P和51V NMR,UV / Vis光谱和ESI-MS光谱所证明的。磷酸容易被取代成四面体的中心位置,表明其他含氧阴离子也可以被类似地取代,从而保证了此类中更丰富的结构。

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