Abstract
In their reduced oxidation states molybdenum and tungsten often show metal-metal (M-M) bonding in both molecular complexes and extended solid state structures. This is particularly true of any highly reduced compounds where the oxidation state is less than four. Whenever electrons are available in the 4d or 5d orbitals these electrons should be considered as valence electrons and may be expected to participate in chemical bonding. For a given oxidation state n+ the metal ion (Mon+ or Wn+) will have a d6-n electron configuration and may form M-M bonds with a maximum bond order sum of 6-n. For example, for Mo3+ structures might be found where each atom forms one M≡M triple bond, three M-M single bonds, six M-M half-bonds, etc. The actual structure adopted will of course depend upon the particular compound, especially the ligand/metal (L/M) ratio. High L/M ratios will of course reduce the possibility that strong M-M bonds can be formed. Compare the contrasting structures of the W2+ compounds (W6Cl8)Cl4 and WCl2(PMe3)4. The former with a L/M ratio of 2 shows a structure with a strongly W-W bonded octahedral cluster unit, whereas the latter with a L/M ratio of 6 exists as a monomeric complex without W-W bonding. In (W6Cl8)Cl4 the d4 electron configuration of W2+ makes possible the formation of the W6 octahedral cluster, where each W atom forms four W-W single bonds.
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References
McCarley R.E., Chapter in Early Transition Metal Clusters with π-Donor Ligands, Chisholm, M. H., Ed., VCH Publishers, New York, NY, 1995, p. 27–61.
Peña O. and Sergent M., Prog. Solid State Chem. 19, 165 (1989).
Chevrel R., Gougeon P., Potel M. and Sergent M., J. Solid State Chem. 57, 25 (1985).
Chevrel R. and Sergent M. in Crystal Chemistry and Properties of Materials with Quasi-One-Dimensional Structures, Rouxel J., Ed., Reidel, Dordrecht, 1986, p. 315.
Hilsenbeck S.J, Young V.G. and McCarley R.E., Inorg. Chem. 33, 1822 (1994).
Zhang X. and McCarley R.E., Inorg. Chem. 34, 2678 (1995).
Saito T., Yamamoto N., Imoto H., J. Am. Chem. Soc. 110, 1646 (1988).
Saito T., Yoshikawa A., Yamakata T., Imoto H. and Unoura K. Inorg. Chem. 28, 3588 (1989).
Saito T., Yamamoto N., Nagase T., Tsuboi T., Kobayashi K., Yamagata T., Imoto H. and Unoura K., Inorg. Chem. 29, 764 (1990).
Xie X. and McCarley R.E, Inorg. Chem, submitted.
Xie X. and McCarley R.E, manuscript in progress.
Spink D., Zhang X., Laughlin S.K., Hur N., Michael J.A. and McCarley R.E., to be published.
Anderson O.K., Klose W. and Nohl H., Phys. Rev. B: Solid State B17, 1209 (1978).
Hughbanks T., Hoffmann R., J. Am. Chem. Soc. 105, 1150 (1983).
Hilsenbeck S.J., McCarley R.E. and Goldman A.I., Chem. Mater. 7, 499 (1995).
McCarley R.E, Hilsenbeck, S.J. and Xie X, J. Solid State Chem. 117, in press.
Torardi C.C. and McCarley R.E., J. Am. Chem. Soc. 101, 3963 (1979).
Mattausch H., Simon A. and Peters E.M., Inorg. Chem. 25, 3428 (1986).
Schimek G.L, Chen S.C. and McCarley R.E., Inorg. Chem, submitted.
Schimek G.L., Nagaki D.A. and McCarley R.E., Inorg. Chem. 33, 1259 (1994).
Schimek G.L. and McCarley R.E., J. Solid State Chem. 113, 345 (1994).
Lii, K.-H. Wang C.C. and Wang S.L., J. Solid State Chem. 77, 407 (1988).
Hibble S.J., Cheetham A.K., Bogle A.R.L., Wakerley H.R. and Cox D.E., J. Am. Chem. Soc. 110, 3295 (1988).
Gall P. and Gougeon P., Acta Crystallogr. C50, 1183 (1994).
Chen S.C. and McCarley R.E., unpublished research.
Gougeon P., Potel M. and Sergent M., Acta Crystallogr. C46, 1188 (1990).
Dronskowski R., Simon A. and Mertin W., Z. Anorg. Allg. Chem. 602, 49 (1991).
Dronskowski R. and Simon A., Acta Chem. Scand. 45, 850 (1991).
Dronskowski R., Mattausch H. and Simon A., Z. Anorg. Allg. Chem. 619, 1397 (1993).
Fais E., Bormann H., Mattausch H. and Simon A., to be published.
Ramlau R., Schimek G.L., Simon A. and McCarley, R.E., to be published.
Wheeler R.A. and Hoffmann R., J. Am. Chem. Soc. 110, 7315 (1988).
Pauling L., The Nature of the Chemical Bond, 3rd Ed, Cornell Univ. Press, Ithaca, NY, 1960, p. 400.
Simon A., Metal-Rich Compounds, Chapter in Solid State Chemistry Compounds, Cheetam A.K. and Day P, Ed, Clarendon Press, Oxford, U.K., 1992.
Corbett J.D. and McCarley R.E, New Transition Metal Halides and Oxides with Extended Metal-Metal Bonding, Chapter in Crystal Chemistry and Properties of Materials with Quasi-One-Dimensional Structures, Rouxel J, Ed, D. Reidel Publishing Co., Dordrecht, 1986, p. 179.
McCarley R.E., Polyhedron 5, 51 (1986).
Hughbanks T. and Hoffmann R., J. Am. Chem. Soc. 105, 3528 (1983).
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McCarley, R.E. (1996). Clusters in Reduced Molybdenum and Tungsten Oxide and Sulfide Systems. In: Schlenker, C., Dumas, J., Greenblatt, M., van Smaalen, S. (eds) Physics and Chemistry of Low-Dimensional Inorganic Conductors. NATO ASI Series, vol 354. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-1149-2_5
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DOI: https://doi.org/10.1007/978-1-4613-1149-2_5
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