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2012 , Vol. 70 >Issue 14: 1555 - 1560

DOI: https://doi.org/10.6023/A12030020

研究论文

Keggin型有机硅取代的多金属氧酸盐衍生物[XW11O40(SiR)2]n-(X=CoIII, P; R=CH=CH2, OH)的合成和表征

  • 张建平 ,
  • 杨春 ,
  • 周家宏
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  • a 江苏省生物功能材料重点实验室 南京师范大学化学与材料科学学院 南京 210097;
    b 江苏省生物功能材料重点实验室 南京师范大学分析测试中心 南京 210097

收稿日期: 2012-03-23

  网络出版日期: 2012-05-03

基金资助

项目受国家自然科学基金(No. 20473037);江苏高校优势学科建设工程和南京师范大学“211工程”三期重点学科建设计划资助.

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Synthesis and Characterization of Organosilyl Derivatives of Keggin Polyoxometalates [XW11O40(SiR)2]n-（X=CoIII, P； R=CH=CH2, OH）

  • Zhang Jianping ,
  • Yang Chun ,
  • Zhou Jiahong
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  • a Jiangsu Key Laboratory of Biofunctional Materials, College of Chemistry and Material Science, Nanjing Normal University, Nanjing 210097;
    b Jiangsu Key Laboratory of Biofunctional Materials, Analysis and Testing Center of Nanjing Normal University, Nanjing 210097

Received date: 2012-03-23

  Online published: 2012-05-03

Supported by

Project supported by the National Natural Science Foundation of China (No. 20473037), the Priority Academic Program Development of Jiangsu Higher Education Institutions and the Leading Academic Discipline Program of 211 Project of Nanjing Normal University (the 3rd phase).

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摘要

以CoIIIW11和有机硅烷为原料, 在pH=1, 乙醇-水(体积比=2:1)的混合溶剂中, 首次合成了Keggin型有机硅取代的钨钴酸盐[CoIIIW11O40(SiR)2]5- (CoIIIW11(SiR)2, R=CH=CH2, OH). 这里, 乙醇作为共溶剂增加硅烷在溶液中的溶解度, 使CoIIIW11在转化为饱和结构之前能够快速与硅烷相遇并反应. 产物的组成和结构用IR, UV-Vis, NMR, TG-DTA, 元素分析等技术进行了全面表征. 结果显示, 两个SiR基团进入了CoIIIW11的空位, 并形成Si—O—Si桥, 得到与先前报道的硅取代钨硅酸盐和钨磷酸盐相似的结构. 还运用此条件成功合成了以往需要在固-液相转移条件下合成的[PW11O40(SiR)2]3- [PW11(SiR)2, R=CH=CH2, OH], 进一步证明了此方法在合成有机硅取代的多金属氧酸盐方面的可行性和通用性.

关键词： 钨钴酸盐; 钨磷酸盐; 有机硅取代; Keggin结构; 合成与表征

本文引用格式

张建平 , 杨春 , 周家宏 . Keggin型有机硅取代的多金属氧酸盐衍生物[XW11O40(SiR)2]n-(X=CoIII, P; R=CH=CH2, OH)的合成和表征[J]. 化学学报, 2012 , 70(14) : 1555 -1560 . DOI: 10.6023/A12030020

Abstract

The Keggin-type organosilyl substituted tungstocobaltates [CoIIIW11O40(SiR)2]5- (CoIIIW11(SiR)2, R=CH=CH2,OH) were synthesized for the first time by using CoIIIW11 and organosilane as starting materials. The syntheses were carried out in an ethanol-water mixing solvent with volume ratio of 2:1 and pH 1. Ethanol was employed as a cosolvent here to increase the solubility of organosilane in the reactive system, so that the organosilane was accessible and could react with CoIIIW11 before it was converted to CoIIIW12. The mixture was stirred at room temperature for 20 h, and then the product was obtained as tetramethylammonium (TMA) salt precipitate by adding tetramethylammonium chloride (TMACl). The structure and composition of the products were characterized by IR, UV-Vis, NMR, TG-DTA and elemental analysis techniques. The IR spectra showed that the Keggin units in the products were close to the saturated structure. Two SiR groups were inserted into the vacancy of CoIIIW11 and a Si—O—Si bridge was formed between two Si atoms, similar to those reported previously in organosilyl substituted tungstosilicate and tungstophosphate. This insertion of SiR groups was also confirmed by 29Si, 1H and 13C NMR of the products, but the 29Si signal exhibited a large chemical shift compared with those of organosilyl substituted tungstosilicate and tungstophosphate possibly due to the paramagnetism of CoIII. UV-Vis spectra of the products also indicated the conversion of the structural symmetry and the retainment of CoIII in the synthesis. The decomposing processes of the products were suggested by TG-DTA curves, which also revealed that, the anion in CoIIIW11(SiOH)2 possesses a higer stability than that in CoIIIW11 (SiCH=CH2)2. Furthermore, [PW11O40(SiR)2]3- [PW11(SiR)2, R=CH=CH2, OH], which were synthesized previously by the procedure of solid-liquid phase transfer, were also synthesized under the same conditions, indicating this method is a feasible and general approach for the synthesis of organosilyl substituted polyoxometalates.

Key words： tungstocobaltates; tungstophosphate; organosilyl substituted; Keggin structure; synthesis and characterization

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