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

doi:10.6023/A12030020

化学学报 ›› 2012, Vol. 70 ›› Issue (14): 1555-1560.DOI: 10.6023/A12030020 上一篇下一篇

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=Co^III, P; R=CH=CH₂, OH)的合成和表征

张建平^a, 杨春^a, 周家宏^b

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

投稿日期:2012-03-23 发布日期:2012-05-03
通讯作者: 杨春 E-mail:yangchun@njnu.edu.cn
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.

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

Zhang Jianping^a, Yang Chun^a, Zhou Jiahong^b

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:2012-03-23 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/Abstract

以Co^IIIW₁₁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[Co^IIIW₁₁O₄₀(SiR)₂]^5- (Co^IIIW₁₁(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Co^IIIW₁₁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Co^IIIW₁₁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

The Keggin-type organosilyl substituted tungstocobaltates [Co^IIIW₁₁O₄₀(SiR)₂]^5- (Co^IIIW₁₁(SiR)₂, R=CH=CH₂,OH) were synthesized for the first time by using Co^IIIW₁₁ 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 Co^IIIW₁₁ before it was converted to Co^IIIW₁₂. 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 Co^IIIW₁₁ 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 Co^III. UV-Vis spectra of the products also indicated the conversion of the structural symmetry and the retainment of Co^III in the synthesis. The decomposing processes of the products were suggested by TG-DTA curves, which also revealed that, the anion in Co^IIIW₁₁(SiOH)₂ possesses a higer stability than that in Co^IIIW₁₁(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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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=Co^III, P; R=CH=CH₂, OH)的合成和表征[J]. 化学学报, 2012, 70(14): 1555-1560.

Zhang Jianping, Yang Chun, Zhou Jiahong. Synthesis and Characterization of Organosilyl Derivatives of Keggin Polyoxometalates [XW₁₁O₄₀(SiR)₂]^n-（X=Co^III, P； R=CH=CH₂, OH）[J]. Acta Chimica Sinica, 2012, 70(14): 1555-1560.

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参考文献

[1] Judeinstein, P. Chem. Mater. 1992, 4, 4.

[2] Judeinstein, P. J. Sol-Gel Sci. Technol. 1994, 2, 147.

[3] Sanchez, C.; de A. A. Soler-Illia, G. J.; Ribot, F.; Lalot, T.; Mayer, C. R.; Cabuil, V. Chem. Mater. 2001, 13, 3061.

[4] Mayer, C. R.; Thouvenot, R.; Lalot, T. Chem. Mater. 2000, 12, 257.

[5] Mayer, C. R.; Thouvenot, R.; Lalot, T. Macromolecules 2000, 33, 4433.

[6] Mayer, C. R.; Cabuil, V.; Lalot, T.; Thouvenot, R. Angew. Chem. Int. Ed. 1999, 38, 3672.

[7] Mayer, C. R.; Cabuil, V.; Lalot, T.; Thouvenot, R. Adv. Mater. 2000, 12, 417.

[8] Schroden, R. C.; Blanford, C. F.; Melde, B. J.; Johnson, B. J. S.; Stein, A. Chem. Mater. 2001, 13, 1074.

[9] Zhang, R. F.; Yang, C. J. Mater. Chem. 2008, 18, 2691.

[10] Luo, X. J.; Yang, C. Phys. Chem. Chem. Phys. 2011, 13, 7892.

[11] Judeinstein, P.; Deprun, C.; Nadjo, L. J. Chem. Soc., Dalton Trans. 1991, 1991.

[12] Knoth, W. H. J. Am. Chem. Soc. 1979, 101, 759.

[13] Ammari, N.; Hervé, G.; Thouvenot, R. New J. Chem. 1991, 15, 607.

[14] Weeks, M. S.; Hill, C. L.; Schinazi, R. F. J. Med. Chem. 1992, 35, 1216.

[15] Agustin, D.; Dallery, J.; Coelho, C.; Proust, A.; Thouvenot, R. J. Organomet. Chem. 2007, 692, 746.

[16] Wang, X. H.; Liu, J. F.; Li, J. X.; Yang, Y.; Liu, J. T.; Li, B.; Pope, M. T. J. Inorg. Biochem. 2003, 94, 279.

[17] Bas-Serra, J.; Todorut, I.; Casa?-Pastor, N.; Server-Carrió, J.; Baker, L. C. W.; Acerete, R. Synth. React. Inorg. Met.-Org. Chem. 1995, 25, 869.

[18] Chen, Y. G.; Liu, J. F. Synth. React. Inorg. Met.-Org. Chem. 1997, 27, 239.

[19] Yang, Q. H.; Dai, H. C.; Liu, J. F. Transition Met. Chem. 1998, 23, 93.

[20] Wu, Q. Y. Mater. Lett. 2000, 42, 179.

[21] Wu, Q. Y.; Sang, X. G.; Shao, F.; Pang, W. Q. Mater. Chem. Phys. 2005, 92, 16.

[22] Yu, X. B.; Wu, H. J. Inorg. Mater. 1996, 11, 703. (余锡宾, 吴虹, 无机材料学报, 1996, 11, 703.)

[23] Wang, E. B.; Hu, C. W.; Xu, L. Introduction to Polyacid Chemistry, Chemical Industry Press, Beijing, 1997, p. 36. (王恩波, 胡长文, 许林, 多酸化学导论, 化学工业出版社, 北京, 1997, p. 36.)

[24] Nomiya, K.; Kobayashi, R.; Miwa, M. Bull. Chem. Soc. Jpn. 1983, 56, 2272.

[25] Kojima, K.; Matsuda, J.; Kojima, N.; Ban, T.; Tsujikawa, I. Bull. Chem. Soc. Jpn. 1987, 60, 3213.

[26] Kojima, K.; Matsuda, J. Bull. Chem. Soc. Jpn. 1985, 58, 821.

[27] Wang, E. B.; Liu, L. L.; Shen, E. H.; Wang, Z. P. Chin. J. Appl. Chem. 1991, 8, 13. (王恩波, 刘连利, 沈恩洪, 王作屏, 应用化学, 1991, 8, 13.)

[28] Wang, E. B.; You, W. S.; Liu, J. F.; Hu, C. W. Chem. J. Chin. Univ. 1991, 12, 711. (王恩波, 由万胜, 刘景福, 胡长文, 高等学校化学学报, 1991, 12, 711.)

[29] Wang, E. B.; Hu, C. W.; Liu, J. F.; Zhang, Y. F. Chin. Sci. Bull. 1991, 36, 197. (王恩波, 胡长文, 刘景福, 张云峰, 科学通报, 1991, 36, 197.)

[30] Acerete, R.; Casa?-Pastor, N.; Bas-Serra, J.; Baker, L. C. W. J. Am. Chem. Soc. 1989, 111, 6049.

[31] Niu, J. Y.; Wang, J. P. Introduction of Heteropoly Compound, Henan University Press, Kaifeng, 2000, p. 350. (牛景扬, 王敬平, 杂多化合物概论, 河南大学出版社, 开封, 2000, p. 350.)

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

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

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