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Organoarsonate Functionalization of Heteropolyoxotungstates
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-11-09 00:00:00 , DOI: 10.1021/acs.inorgchem.7b01928
Xiaofeng Yi 1, 2 , Natalya V. Izarova 1 , Paul Kögerler 1, 2
Affiliation  

Functionalization of the {P8W48} polyoxotungstate (POT) archetype with aromatic organoarsonates results in the first homometallic {P8W48} derivatives, with the general formula [(RAsVO)4PV8WVI48O184]32− [R = C6H5 (1) or p-(H2N)C6H4 (2)]. Short As−O bonds here induce unusual bending of the otherwise rigid {P8W48} macrocycle, breaking its D4h symmetry. The obtained species also represent the first lacunary POTs functionalized with organoarsonates and can potentially act as polyoxometalate precursors themselves. We elaborate solution stability in different aqueous media using 1H and 31P NMR spectroscopy and possible pathways for subsequent transformations in aqueous solutions of the functionalized polyanions. Recrystallization of the K+/Li+/dimethylammonium salt of 2 from 4 M LiCl solution yielded a further functionalized POT, [(H3NC6H4AsO)3P8W48O184Hx{WO2(H2O)2}0.4](30.2−x)− (3), revealing dissociation of the organoarsonate fragments in slightly acidic aqueous solutions followed by their rearrangement within the inner POT cavity.

中文翻译:

杂多氧钨酸盐的有机磺酸盐官能化。

将{P 8 W 48 }聚氧钨酸盐(POT)原型与芳族有机砷酸盐官能化,得到第一批均金属{P 8 W 48 }衍生物,其通式为[(RAs V O)4 P V 8 W VI 48 O 184 ]。32- [R = C 6 H 51)或p-(H 2 N)C 6 H 42)]。短的As-O键会引起原本坚硬的{P 8 W 48}大环,打破了其D 4 h对称性。所获得的物质还代表了首个用有机砷酸盐官能化的凹腔POT,它们本身也可能充当多金属氧酸盐的前体。我们使用1 H和31 P NMR光谱阐述了在不同水性介质中的溶液稳定性,以及功能化聚阴离子在水溶液中后续转化的可能途径。K个的再结晶+ /锂+的/二甲基铵盐2从4M的LiCl溶液产生了进一步官能POT,[(H 3 NC 6 H ^ 4 ASO)3 P 8W 48 O 184 H x {WO 2(H 2 O)2 } 0.4 ] (30.2- x)-3),显示有机砷酸盐片段在弱酸性水溶液中解离,然后在内部POT腔内重新排列。
更新日期:2017-11-09
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