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5 - Main-group–transition-metal clusters

Published online by Cambridge University Press:  19 February 2010

Thomas Fehlner ,
Jean-Francois Halet  and
Jean-Yves Saillard
Thomas Fehlner
Affiliation:
University of Notre Dame, Indiana
Jean-Francois Halet
Affiliation:
Université de Rennes I, France
Jean-Yves Saillard
Affiliation:
Université de Rennes I, France
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Summary

A large number of mixed main-group–transition-metal clusters can be understood with isolobal ideas and the electron-counting rules. However, there is a growing number that cannot. These clusters are more closely related to metal clusters than main-group clusters. In this chapter we begin with a survey of the “rule-abiding” mixed-element clusters with emphasis on variety rather than comprehensiveness. Why a cursory survey? Because with a solid background of main-group and transition-metal cluster behavior under our belts, the isolobal analogy permits a ready understanding of mixed systems that follow the rules. Understanding permits prediction of possible stoichiometry and structure thereby generating goals for future synthesis.

It is the second compound type that constitutes an interesting challenge to our views of cluster electronic structure. With this compound type we encounter a structural response arising from main-group and transition-metal atom competition within the context of a molecular cluster. This competition generates both cluster shapes invariant to change in electron count as well as new cluster-structure types associated with unusual electron counts. Both pose a problem of interpretation. But the problem is a worthwhile one as structures that deviate from the electron-counting rules contain information on the electronic factors that underlie cluster chemistry in general. “Failure” of the rules actually constitutes a gateway leading to compounds with hybrid properties not accessible with either pure main-group or transition-metal clusters. Useful chemistry is all about properties and the more ways we develop to vary and control properties the better off we are.

Type
Chapter
Information
Molecular Clusters
A Bridge to Solid-State Chemistry
 , pp. 165 - 204
Publisher: Cambridge University Press
Print publication year: 2007

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References

Williams, R. E. (1976). Adv. Inorg. Chem. and Radiochem., 18, 67.CrossRef
Chung, J.-H., Knoeppel, D., McCarthy, D., Columbie, A. and Shore, S. G. (1993). Inorg. Chem., 32, 3391.CrossRef
Housecroft, C. E. (1992). In Inorganometallic Chemistry, Fehlner, T. P., (Ed.). New York: Plenum Press, p. 73.CrossRefGoogle Scholar
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Charles, S., Eichhorn, B. W., Rheingold, A. L. and Bott, S. G. (1994). J. Am. Chem. Soc., 116, 8077.CrossRef
Kesanli, B., Fettinger, J. and Eichhorn, B. W. (2001). Chem. Eur. J., 7, 5277.3.0.CO;2-C>CrossRef
Halet, J.-F., Hoffmann, R. and Saillard, J.-Y. (1985). Inorg. Chem., 24, 1695.CrossRef
Kennedy, J. D. (1998). In The Borane, Carborane, Carbocation Continuum, Casanova, J. (Ed.). New York: Wiley, p. 85.Google Scholar
Littger, R., English, U., Ruhlandt-Senge, K. and Spencer, J. T. (2000). Angew. Chem. Int. Ed., 39, 1472.3.0.CO;2-9>CrossRef
Baker, R. T. (1986). Inorg. Chem., 25, 109.CrossRef
Johnston, R. L., Mingos, D. M. P. and Sherwood, P. (1991). New J. Chem., 15, 831.
Le, Guennic B., Jiao, H., Kahal, S., Saillard, J.-Y., Halet, J.-F., Ghosh, S., Shang, M., Beatty, A. M., Rheingold, A. L. and Fehlner, T. P. (2004). J. Am. Chem. Soc., 126, 3203.
Reddy, A. C., Jemmis, E. D., Scherer, O. J., Winter, R., Heckmann, G. and Wolmershäuser, G. (1992). Organometallics, 11, 3894.CrossRef
Callahan, K. P., Evans, W. J., Lo, F. Y., Strouse, C. E. and Hawthorne, M. F. (1975). J. Am. Chem. Soc., 97, 296.CrossRef
Moses, M. J., Fettinger, J. C. and Eichhorn, B. W. (2003). Science, 300, 778.CrossRef
Trinh-Toan, , Teo, B. K., Ferguson, J. A., Meyer, T. J. and Dahl, L. F. (1977). J. Am. Chem. Soc., 99, 408.CrossRef
Harris, S. (1989). Polyhedron, 8, 2843.CrossRef
Klausmeyer, K. K., Wilson, S. R. and Rauchfuss, T. B. (1999). J. Am. Chem. Soc., 121, 2705.CrossRef
Wang, S., Zuo, J.-L., Zhou, H.-C., Choi, H. J., Ke, Y., Long, J. R. and You, X.-Z. (2004). Angew. Chem. Int. Ed., 43, 5940.CrossRef
Burdett, J. K. and Miller, G. J. (1987). J. Am. Chem. Soc., 109, 4081.CrossRef
Fenske, D., Ohmer, J., Hachgenei, J. and Merzweiler, K. (1988). Angew. Chem. Int. Ed., 27, 1277.CrossRef
Halet, J.-F. and Saillard, J.-Y. (1999). Metal Clusters in Chemistry, Braunstein, Oro, P. L. and Raithby, P. R. (Eds.), Vol. 3. Weinheim: Wiley-VCH, p. 1643.
Williams, R. E. (1976). Adv. Inorg. Chem. and Radiochem., 18, 67.CrossRef
Chung, J.-H., Knoeppel, D., McCarthy, D., Columbie, A. and Shore, S. G. (1993). Inorg. Chem., 32, 3391.CrossRef
Housecroft, C. E. (1992). In Inorganometallic Chemistry, Fehlner, T. P., (Ed.). New York: Plenum Press, p. 73.CrossRefGoogle Scholar
Whitmire, K. (1988). J. Coord. Chem., 17, 95.CrossRef
Charles, S., Eichhorn, B. W., Rheingold, A. L. and Bott, S. G. (1994). J. Am. Chem. Soc., 116, 8077.CrossRef
Kesanli, B., Fettinger, J. and Eichhorn, B. W. (2001). Chem. Eur. J., 7, 5277.3.0.CO;2-C>CrossRef
Halet, J.-F., Hoffmann, R. and Saillard, J.-Y. (1985). Inorg. Chem., 24, 1695.CrossRef
Kennedy, J. D. (1998). In The Borane, Carborane, Carbocation Continuum, Casanova, J. (Ed.). New York: Wiley, p. 85.Google Scholar
Littger, R., English, U., Ruhlandt-Senge, K. and Spencer, J. T. (2000). Angew. Chem. Int. Ed., 39, 1472.3.0.CO;2-9>CrossRef
Baker, R. T. (1986). Inorg. Chem., 25, 109.CrossRef
Johnston, R. L., Mingos, D. M. P. and Sherwood, P. (1991). New J. Chem., 15, 831.
Le, Guennic B., Jiao, H., Kahal, S., Saillard, J.-Y., Halet, J.-F., Ghosh, S., Shang, M., Beatty, A. M., Rheingold, A. L. and Fehlner, T. P. (2004). J. Am. Chem. Soc., 126, 3203.
Reddy, A. C., Jemmis, E. D., Scherer, O. J., Winter, R., Heckmann, G. and Wolmershäuser, G. (1992). Organometallics, 11, 3894.CrossRef
Callahan, K. P., Evans, W. J., Lo, F. Y., Strouse, C. E. and Hawthorne, M. F. (1975). J. Am. Chem. Soc., 97, 296.CrossRef
Moses, M. J., Fettinger, J. C. and Eichhorn, B. W. (2003). Science, 300, 778.CrossRef
Trinh-Toan, , Teo, B. K., Ferguson, J. A., Meyer, T. J. and Dahl, L. F. (1977). J. Am. Chem. Soc., 99, 408.CrossRef
Harris, S. (1989). Polyhedron, 8, 2843.CrossRef
Klausmeyer, K. K., Wilson, S. R. and Rauchfuss, T. B. (1999). J. Am. Chem. Soc., 121, 2705.CrossRef
Wang, S., Zuo, J.-L., Zhou, H.-C., Choi, H. J., Ke, Y., Long, J. R. and You, X.-Z. (2004). Angew. Chem. Int. Ed., 43, 5940.CrossRef
Burdett, J. K. and Miller, G. J. (1987). J. Am. Chem. Soc., 109, 4081.CrossRef
Fenske, D., Ohmer, J., Hachgenei, J. and Merzweiler, K. (1988). Angew. Chem. Int. Ed., 27, 1277.CrossRef
Halet, J.-F. and Saillard, J.-Y. (1999). Metal Clusters in Chemistry, Braunstein, Oro, P. L. and Raithby, P. R. (Eds.), Vol. 3. Weinheim: Wiley-VCH, p. 1643.

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