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Modification of Metal Alkoxide Precursors by Organofunctional Bidentate Ligands: Chemical Problems and Opportunities for Materials Syntheses

Published online by Cambridge University Press:  01 February 2011

Ulrich Schubert ,
Ulrike Bauer ,
Helmut Fric ,
Michael Puchberger ,
Wolfgang Rupp  and
Viktoria Torma
Ulrich Schubert
Affiliation:
Institute of Materials Chemistry, Vienna University of Technology Getreidemarkt 9/165, A-1060 Wien, Austria
Ulrike Bauer
Affiliation:
Institute of Materials Chemistry, Vienna University of Technology Getreidemarkt 9/165, A-1060 Wien, Austria
Helmut Fric
Affiliation:
Institute of Materials Chemistry, Vienna University of Technology Getreidemarkt 9/165, A-1060 Wien, Austria
Michael Puchberger
Affiliation:
Institute of Materials Chemistry, Vienna University of Technology Getreidemarkt 9/165, A-1060 Wien, Austria
Wolfgang Rupp
Affiliation:
Institute of Materials Chemistry, Vienna University of Technology Getreidemarkt 9/165, A-1060 Wien, Austria
Viktoria Torma
Affiliation:
Institute of Materials Chemistry, Vienna University of Technology Getreidemarkt 9/165, A-1060 Wien, Austria
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Abstract

Bidentate ligands are potentially useful to modify metal alkoxides precursors for sol-gel processing. However, anionic bidentate ligands are needed to get a strong coordination, while diamines as neutral bidentate ligand form coordination polymers [Ti2(OR)8(diamine)2]∞ when reacted with Ti(OR)4. The Lewis acidity of metal alkoxides may cause organic side reactions. The first is the formation of ester and water in the reaction with carboxylic acids, and therefore carboxylate-substituted metal oxide clusters of the general composition MnOx(OH/OR)y(OOCR)z are obtained instead of substituted monomeric precursors. The second side reaction discussed is the cleavage of β-diketones by metal alkoxides. Despite this side reaction, 3-acetyl-6-trimethoxy-silyl-hexane-2-one is a useful compound to prepare single-source precursos for silica/metal oxide composites.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 847: Symposium EE – Organic/Inorganic Hybrid Materials , 2004 , EE7.2
Copyright
Copyright © Materials Research Society 2005

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References

REFERENCES

1. (a) Livage, J., Henry, M. and Sanchez, C., Progr. Solid State Chem. 18, 259 (1988).Google Scholar
(b) Sanchez, C. and Livage, J., New J. Chem. 14, 413 (1990).Google Scholar
2. Schubert, U., J. Sol-Gel Sci. Technol. 26, 47 (2003).Google Scholar
3. (a) Vaartstra, B. A., Huffman, J. C., Gradeff, P. S., Hubert-Pfalzgraf, L. G., Daran, J. C., Parraud, S., Yunlu, K. and Caulton, K. G., Inorg. Chem. 29, 3126 (1990).Google Scholar
(b) Campbell, C., Bott, S. G., Larsen, R. and van der Sluys, W. G., Inorg. Chem. 33, 4950 (1994).Google Scholar
4. Veith, M., Mathur, S., Mathur, C. and Huch, V., J. Chem. Soc. Dalton 2101 (1997).Google Scholar
5. Fric, H. and Schubert, U., New J. Chem. in press.Google Scholar
6. Crystallographic data: space group P-1, a = 880.3(2), b = 903.6(2), c = 1156.3(2) pm, α = 101.675(4), β = 101.566(4), β = 114.559(3). Crystallographic data have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 255309. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44–1223/336033; E-mail: ).Google Scholar
7. Schubert, U., Tewinkel, S. and Möller, F., Inorg. Chem. 34, 995 (1995).Google Scholar
8. Errington, R. J., Ridland, J., Clegg, W., Coxall, R. A. and Sherwood, J. M., Polyhedron 17, 659 (1998).Google Scholar
9. Fric, H., Kogler, F. R., Puchberger, M. and Schubert, U., Z. Naturforsch. B, (2004) in press.Google Scholar
10. Boyle, T. J., Rodriguez, M. A. and Alam, T. M., J. Chem. Soc. Dalton Trans. 4598 (2003).Google Scholar
11. Kickelbick, G., Feth, M. P., Bertagnolli, H., Puchberger, M., Holzinger, D. and Gross, S., J. Chem. Soc. Dalton 3892 (2002).Google Scholar
12. For an overview see: Schubert, U. in Compr. Coord. Chem. II, Vol.7, edited by Fujita, M., Powell, A. and Creutz, C.A., Elsevier, 2003, p. 629.Google Scholar
13. Schubert, U., Arpac, E., Glaubitt, W., Helmerich, A. and Chau, C., Chem. Mater. 4, 291 (1992).Google Scholar
14. (a) Kickelbick, G. and Schubert, U., Eur. J. Inorg. Chem. 159 (1998).Google Scholar
(b) Kickelbick, G., Wiede, P. and Schubert, U., Inorg. Chim. Acta 284, 1 (1999).Google Scholar
15. (a) Guerrero, G., Mehring, M., Mutin, P. H., Dahan, F. and Vioux, A., J. Chem. Soc. Dalton 1537 (1999).Google Scholar
(b) Mehring, M., Schurmann, M., Mutin, P. H. and Vioux, A., Z. Kristallogr. 215, 591 (2000).Google Scholar
(c) Mehring, M., Guerro, G., Dahan, F., Mutin, P. and Vioux, A., Inorg. Chem. 39, 3325 (2000).Google Scholar
(d) Mutin, P. H., Mehring, M., Guerrero, G. and Vioux, A., Mat. Res. Soc. Symp. Ser. 628, CC2.4.1 (2001).Google Scholar
16. (a) Schubert, U., Chem. Mater. 13, 3487 (2001).Google Scholar
(b) Kickelbick, G., Schubert, U., Monatsh. Chem. 132, 13 (2001).Google Scholar
(c) Kickelbick, G., Schubert, U. in Synthesis, Functionalization and Surface Treatment of Nanoparticles, edited by Baraton, M.-I., Amer. Sci. Publ., Stevenson Ranch, 2003, p. 91.Google Scholar
17. Kickelbick, G., Holzinger, D., Brick, C., Trimmel, G. and Moons, E., Chem. Mater. 14, 4382 (2002).Google Scholar
18. Kogler, F. R., Jupa, M., Puchberger, M. and Schubert, U., J. Mater. Chem. 14, 3133 (2004).Google Scholar
19. (a) Urbaniak, W. and Schubert, U., Liebigs Ann. Chem. 1221 (1991).Google Scholar
(b) Puchberger, M., Rupp, W., Bauer, U. and Schubert, U., New J. Chem. 28, 1289 (2004).Google Scholar
20. Hoebbel, D., Reinert, T., Schmidt, H. and Arpac, E., J. Sol-Gel Sci. Technol. 10, 115 (1997).Google Scholar
21. Puchberger, M., Rupp, W., Bauer, U. and Schubert, U., New J. Chem. 28, 1289 (2004).Google Scholar
22. Poncelet, O., Hubert-Pfalzgraf, L. and Daran, J.-C., Polyhedron 9, 1305 (1990).Google Scholar
23. Rupp, W., Hüsing, N. and Schubert, U., J. Mater. Chem. 12, 2594 (2002).Google Scholar
24. Torma, V., Peterlik, H., Bauer, U., Rupp, W., Hüsing, N., Bernstorff, S., Steinhart, M., Görigk, G. and Schubert, U., Chem. Mater. submitted.Google Scholar