Hostname: page-component-586b7cd67f-dlnhk Total loading time: 0 Render date: 2024-11-25T15:36:10.024Z Has data issue: false hasContentIssue false

Molecular Routes to Tin Oxides

Published online by Cambridge University Press:  28 February 2011

T.A. Wark
Affiliation:
Department of Chemistry and Center for Micro-Engineered Ceramics, University of New Mexico, Albuquerque, NM 87131.
E.A. Gulliver
Affiliation:
Department of Chemistry and Center for Micro-Engineered Ceramics, University of New Mexico, Albuquerque, NM 87131.
L.C. Jones
Affiliation:
Department of Chemistry and Center for Micro-Engineered Ceramics, University of New Mexico, Albuquerque, NM 87131.
M.J. Hampden-Smith
Affiliation:
Department of Chemistry and Center for Micro-Engineered Ceramics, University of New Mexico, Albuquerque, NM 87131.
A.L. Rheingold
Affiliation:
Department of Chemistry, University of Delaware, Newark, DE 19716.
J.C. Huffman
Affiliation:
Molecular Structure Center, Indiana University, Bloomington, IN 47405.
Get access

Abstract

A general route to low temperature synthesis of ternary metal tin oxides with controlled stoichiometries from single component molecular metal alkoxide precursors is described. The solid state and solution structures of homoleptic tin(IV) alkoxide compounds have been investigated to establish criteria for the determination of their solution structure. Tin alkoxide compounds suitable for metathesis reactions have been synthesized and used to prepare the mixed metal alkoxide compounds [ZnSn(OEt)6] and [((COD)Rh)2Sn(OEt)6] (where Et = ethyl and COD = 1,5-cyclooctadiene). Hydrolysis of [ZnSn(OEt)6] at neutral pH results in the formation of a high surface area, mainly amorphous hydrous oxide powder which forms Zn2SnO4 and SnO2 on heating to 600°C and ZnSnO3 on heating to 1000°C.Thermolysis of [((COD)Rh}2Sn(OEt)6] results in formation of rhodium and tin(IV) oxide (cassiterite phase).

Type
Research Article
Copyright
Copyright © Materials Research Society 1990

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1a. Hsu, H.M., Yee, I., DeLuca, J., Hilbert, C., Miralky, R.F. and Smith, N.L., Appl. Phys. Lett., 54, 957, 1989:Google Scholar
1b. Gupta, A., Cooper, E.I., Jagannathan, R. and Geiss, E.A., ACS symposium series No. 377, “Chemistry of High Tc Superconductors”, George, T.T. and Nelson, D.L. Eds.:Google Scholar
1c. “Better Ceramics Through Chemistry III” Part IV, Brinker, C.J., Clark, D.E. and Ulrich, D.R., Eds., MRS symposium proceedings, 1988:Google Scholar
1d. Goel, S.C., Kramer, K.S., Gibbons, P.C. and Buhro, W.E., Inorg. Chem., 28, 3619, 1989.Google Scholar
2a. Debsikerdar, J.C., J. Mat. Sci., 20, 4454, 1985:Google Scholar
2b. Blum, J.B. and Gurkovich, S.R., J. Mat. Sci., 20, 4479, 1985:Google Scholar
2c. Rehspringer, J.L., El Hagigui, S., Vilminot, S., Poix, P. and Beringer, J.C. in “Ultrastructure Processing of Advanced Ceramics”, Mackenzie, J.D. Ulrich, D.R., Eds, Wiley, 1988:Google Scholar
2d. Ulrich, D.R., J. Non-cryst. Solids, 100, 174, 1988:Google Scholar
2e. Mackenzie, J., J. Non-cryst. Solids, 100, 162, 1988:Google Scholar
2f. Wu, E., Chen, K.C. and Mackenzie, J.D. in “Better Ceramics Through Chemistry”, Brinker, C.J., Clark, D.E. and Ulrich, D.R., Eds., MRS symposium proceedings, 1984.Google Scholar
3a. Bradley, D.C., Chem. Rev., 89, 1317, 1989:Google Scholar
3b. Hubert-Pfaltzgraf, L.G., New J. Chem., 11, 663, 1987.Google Scholar
4. Anderson, H., Kodas, T.T. and Smith, D.M., Cer. Bull., 68, 996, 1989.Google Scholar
5. “Better Ceramics Through Chemistry III”, Brinker, C.J., Clark, D.E. and Ulrich, D.R., Eds., MRS symposium proceedings, 1988.Google Scholar
6a. Bradley, D.C., Mehrotra, R.C. and Gaur, D.P. in “Metal Alkoxides” Academic press, 1978:Google Scholar
6b. Klemperer, W.G., Mainz, V.V., Ramanmurti, S.D. and Rosenburg, F.S., in “Better Ceramics Through Chemistry III”, Brinker, C.J., Clark, D.E. and Ulrich, D.R., Eds., MRS symposium proceedings, 1988:Google Scholar
6c. Riman, R.E., Haaland, D.M., Northrup, C.J.M., Bowen, H.K. and Bleier, A., Mat. Res. Soc. Symp. Proc., Vol. 32, 233, 1984:Google Scholar
6d. Fukushima, J., Kodaira, K., Matsushita, T., Ceramic Bulletin, 55, 1064, 1976:Google Scholar
6e. Kirbir, F. and Komiyama, H., Chem. Lett., 791, 1988:Google Scholar
6f. Shiota, F.M., J. Mat. Sci., 23, 1718, 1988.Google Scholar
7. Smith, J.S., Dollof, R.T. and Mazdiyasni, K.S., J. Am. Cer. Soc., 91, 53, 1970.Google Scholar
8a. Yanovskaya, M.I., Turevskaya, E.P., Leonov, A.P., Ivanov, S.A., Kolganova, M.V., Stefanovich, S.Y., Turiva, N.Y. and Venevtsev, Y.N., J. Mat. Sci., 23, 395, 1988:Google Scholar
8b. Rousett, A., Chassagneux, F. and Paris, J., J. Mat. Sci., 21, 3111, 1986:Google Scholar
8c. Bradley, D.C. and Patel, A.K. in reference 3.Google Scholar
9. It has been demonstrated that tin(IV) alkoxide compounds can be used as precursors for the formation of high purity SnO2 powders, I.M. Thomas, U.S. patent 3,946,056, July 25th, 1974. Tin(IV) oxide is commonly prepared by hydrolysis of SnC14 in aqueous ammonia, but the retention of halide impurities often plague this method,Google Scholar
9a. Harrison, P.G. and Maunders, B.M., J. Chem. Soc., Faraday Trans., 80, 1341, 1984,Google Scholar
9b. and references therein.Google Scholar
10. Shriver, D.F. and Dresden, M.A., “The Manipulation of Air Sensitive Compounds” 2nd Edition, Wiley Interscience, 1986, p 78.Google Scholar
11. Burfield, D.R. and Smithers, R.H., J. Org. Chem., 48, 2420, 1983.Google Scholar
12. Chandler, C.D., Fallon, G.D., Koplick, A.J. and West, B.O., Aust. J. Chem., 40, 1427, 1987.Google Scholar
13. Shoemaker, D.P., Garland, C.W. and Steinfield, J.I., “Experiments in Physical Chemistry” 3rd Ed., McGraw-Hill Book Company, p 174185, 1974.Google Scholar
14a. Bradley, D.C., Caldwell, E.A.V. and Wardlaw, W., J. Chem. Soc., A., 4775, 1957:Google Scholar
14b. Thomas, I.M., Can. J. Chem., 39, 1386, 1961.Google Scholar
15. Hampden-Smith, M.J., Wark, T.A., Rheingold, A.L. and Huffman, J.C., Can. J. Chem., submitted for publication.Google Scholar
16a. Bradley, D.C., Mehrotra, R.C., Swanwick, J.D. and Wardlaw, W., J. Chem. Soc., 5020, 1952.:Google Scholar
16b. K.G. Caulton private communication.Google Scholar
17. Using a simplified “diatomic molecule” approach, the v(Sn-O) stretching frequency was calculated to be 580 cm−1 by treating labelled and unlabelled tertiary butoxide groups as point masses of 82 and 73, respectively. This assumption has previously yielded satisfactory results in analogous 18Olabelling experiments. Bradley, D.C. and Westlake, A.H., “Proc. Symp. Coord. Chem.,” Tihany, Hungary, published by the Hungarian Acad. Sci., Budapest, 309, 1965, referred to in reference 6a.Google Scholar
18. Hampden-Smith, M.J., Smith, D.E. and Duesler, E.N., Inorg. Chem., 28, 339, 1989.Google Scholar
19. Wark, T.A., Gulliver, E.A., Hampden-Smith, M.J. and Rheingold, A.L., Inorg. Chem., submitted for publication.Google Scholar
20a. Veith, M. and Rosler, R., Z. Naturforsch, 4lb, 1017, 1986:Google Scholar
20b. Veith, M. and Rosler, R., Angew. Chem., Int. Ed., Engl., 21, 858, 1982.Google Scholar
21. Wark, T.A. and Hampden-Smith, M.J., unpublished results. We note that similar compounds have previously been prepared, e.g. LiSn2(OR)9 , see ref. 6a.Google Scholar
22. It has previously been reported that thermal decomposition of metal alkoxide compounds results in formation of alcohol and alkene, Bradley, D.C. and Faktor, M.M., Trans. Faraday Soc., 55, 2117, 1959:Google Scholar
22a. Bradley, D.C. and Faktor, M.M., J. Appl. Chem., 9, 435, 1959:Google Scholar
22b. Stecher, H.A., Sen, A. and Rheingold, A.L., Inorg. Chem., 28, 3280, 1989.Google Scholar
22c. An exception has recently been reported, Jeffries, P.M. and Girolami, G.S., Chem. Mat., 1, 8, 1989.Google Scholar
23. Similar cyclodecadienes have been prepared by Wilke, et al. . at nickel centers,Google Scholar
23a. see e.g. Heimbach, P. and Wilke, G., Liebigs Ann. Chem. 727, 183, 1969 Google Scholar
23b. and 727, 194, 1969:Google Scholar
23c. Wilke, G., Angew. Chem., Int. Ed. Engl., 2, 105, 1963.Google Scholar