Abstract
The possibility of connections between the properties of clusters on the one hand and surfaces on the other has stimulated a considerable amount of research in the area of cluster chemistry. [13] Much has concerned structure (geometric and electronic) and spectroscopic properties and the successes have been detailed elsewhere. [4, 5] Hence, it is highly appropriate that the other half of cluster chemistry, that concerned with reactivity, be examined in light of possible connections with surface reactivity. What follows is a review of studies of cluster reactivity, mainly drawn from our own work, with an emphasis on its relevance to the reactivity of molecules on surfaces.
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References
Gonzalez-Moraga, G. (1993) Cluster Chemistry .Introduction to Transition Metal and Main Group Element Clusters, Springer Verlag, New York.
Shriver, D. F., Kaesz, H. D. and Adams, R. D. (1990) The Chemistry of Metal Cluster Complexes ,VCH, New York.
Johnson, B. F. G. and Lewis, J. (1981) Transition metal clusters, Adv. Inorg. Chem. Radiochem. 24, 225.
Gates, B., Guczi., L. and Knozinger, H., (1986) Studies in Surface Science and Catalysis ,Elsevier, New York.
Muetterties, E. L., Rhodin, T. N., Band, E., Brucker, C. F. and Pretzer, W. R. (1979) Clusters and surfaces, Chem. Rev. 79, 91.
Fontijn, A. and Clyne, M. A. A. (1983) Reactions of Small Transient Species ,Academic Press, New York.
Rhodin, T. N. and Ertl, G. (1979) The Nature of the Surface Chemical Bond ,North-Holland, New York.
Somorjai, G. A. (1981) Chemistry in Two Dimensions: Surfaces ,Cornell Univ. Press, Ithaca.
Bent, B. E., Nuzzo, R. G. and Dubois, L. H. (1989) Surface organometallic chemistry in the chemical vapor deposition of aluminum films using triisobutylaluminun. ß-Hydride and ß-alkyl elimimination reactions of surface alkyl intermediates, J. Am. Chem. Soc. 111,1634.
Mason, R. (1976/77) The Evolution of a coordination and organometallic chemistry of surfaces, Israel J. Chem. 15, 174.
Sailor, M. J., Went, M. J. and Shriver, D. F. (1988) Characteristic vibrational frequencies and normal modes of the CCO ligand in trinuclear ketenylidene clusters, Inorg. Chem. 27, 2666.
Moskovits, M. (1979) metal cluster complexes and heterogeneous catalysis-A heterodox view, Accts. Chem. Research 12, 229.
Fehlner, T. P. (1992) Inorganometallic Chemistry ,Plenum, New York.
Spielvogel, B. F. (1980) Synthesis and biological activity of boron analogues of the a-amino acids and related compounds, Pergamon Press, Oxford.
Fehlner, T. P. (1988) Metal-rich ferra-and cobaltaboranes. Mimics of organometallic clusters, New J. Chem. 12, 307.
Muetterties, E. L. (1982) Hydrocarbon reactions at metal centres, Chem. Soc. Rev. 11, 283.
Dutta, T. K., Vites, J. V., Jacobsen, G. B. and Fehlner, T. P. (1987) The making and breaking of C-H bonds on a metal cluster framework. analysis of the tautomerization and deprotonation of Fe3(CO)9CH4 leading to the interconversion of FeHFe and CHFe interactions, Organometallics 6, 842.
Wong, S. W. and Fehlner, T. P. (1981) Preparation of H3Fe3(CO)9CCH3 from Fe(CO)5, J. Am. Chem. Soc. 103,966.
Carty, A. J., Johnson, B. F. G., Lewis, J. and Norton, J. R. (1972) The synthesis of H3Ru3(CO)9CCH3, a ruthenium ethylidyne complex, J Chem. Soc. Dalton Trans477.
Vites, J. C., Housecroft, C. E., Eigenbrot, C, Buhl, M. L., Long, G. J. and Fehlner, T. P. (1986) The structure and properties of HFe3(CO)9BH3R and the conjugate bases [HFe3(CO)9BH2R]-(R=H CH3), J. Am. Chem. Soc. 108, 3304.
Vites, J. C., Eigenbrot, C. and Fehlner, T. P. (1984) The preparation and characterization of HFe3(CO)9H3BH, J. Am. Chem. Soc. 106,4633.
Chipperfield, A. K. and Housecroft, C. E. (1988) The preparation of the metal-rich ruthenaborane, Ru3(CO)9BH5: a case of isomerisation involving endo-hyfaogtn migration, J. Organomet. Chem. 349,C17.
Beno, M. A., Williams, J. ML, Tachikawa, M. and Muetterties, E. L. (1981) The closed three-center carbon-hydrogen-metal interaction. A neutron diffraction study of HFe4(2-CH)(CO)12, J. Am. Chem. Soc. 103, 1485.
Cowie, A. G., Johnson, B. F. G., Lewis, J. and Raithby, P. R. (1986) Structural isomers of H2Ru4C(CO)12 X-ray crystal structure of Ru4C(CO)13, J. Organomet. Chem. 306, C 63.
Rath, N. P. and Fehlner, T. P. (1987) Multiple deprotonation of a ferraborane. Evidence for the formation of a discrete transition-metal boride, J. Am. Chem. Soc. 109,5273.
Hong, F. E., McCarthy, D. A., White III, J. P., Cottrell, C. E. and Shore, S. G. (1990) Reaction, of THF.BH3 with H2Ru4(CO)13 and H4Ru4(CO)12 Preparation and structure of HRu(CO)12BH2, Inorg. Chem. 29, 2874.
Housecroft, C. E. (1992) Transition metal main group cluster compounds, in T. P. Fehlner (ed), Inorganometallic Chemistry ,Plenum Press, New York.
Lynam, M. M., Chipman, D. M., Barreto, R. D. and Fehlner, T. P. (1987) Endo hydrogens on main group-transition metal clusters. Theoretical analysis of the interconversion of FeHFe and EHFe interactions and deprotonation of Fe3(CO)9EHx (E = B, X = 5
Mingos, D. M. P. and Wales, D. J. (1990) Introduction to Cluster Chemistry ,Prentice Hall, New York.
Brookhart, M. and Green, M. L. H. (1983) C -H -transition metal bonds, J. Organomet. Chem. 250,395.
Brookhart, M., Green, M. L. H. and Wong, L.-L. (1988) Carbon hydrogen transition metal bonds, Prog. Inorg. Chem. 36,1.
Fehlner, T. P. (1990) On the energetics of the formation of E-H-M for M-H-M interactions on transition metal clusters, Polyhedron 9, 1955.
Shore, S. G., Jan, D.-Y., Hsu, L.-Y. and Hsu, W.-L. (1983) Insertion of boron into an osmium-carbonyl bond. Preparation and crystal structure of the carbonyl borylidyne H3(CO)90s3BCO, J Am. Chem. Soc. 105, 5923.
Jan, D.-Y., Workman, D. P., Hsu, L.-Y., Krause, J. A. and Shore, S. G. (1992) Clusters derived from the hydroboration of (Li-H)20s3(CO)10nd their derivatives, Inorg. Chem. 31, 5123.
Crascall, L. E., Thimmappa, B. H. S., Rheingold, A. L., Ostrander, R. and Fehlner, T. P. (1994) Synthesis of [AsPh4][Fe3(CO)9(CO)(HBCl)] by oxidative chloride substitution of [Fe3(CO)9(HBCO)]2-, Organometallics 13, 0000.
Jun, C.-S. (1994) Synthesis of New Metallaboranes, Thesis, University of Notre Dame,
Barreto, R. D., Puga, J. and Fehlner, T. P. (1990) Electronic and steric control of the formation of CHM from MHM interactions in carbon atom capped transition metal carbonyl clusters. Effect of the metal fragment, Organometallics 9, 662.
Vites, J. and Fehlner, T. P. (1984) A facile equilibrium involving CO and H2. The Fe-H-Fe bond energy in H3Fe3(CO)9CMe, Organometallics 3, 491.
Dutta, T. K., Meng, X., Vites, J. C. and Fehlner, T. P. (1987) Reactions of H3Fe3(CO)9CMe. H2 displacement by CO and H2elimination following deprotonation, Organometallics 6, 2191.
Bandyopadhyay, A. K., Khattar, R. and Fehlner, T. P. (1989) Skeletal rearrangement of Rh3Fe4(CO)i6B“. An example of an associative cluster isomerization, Inorg. Chem. 28, 4434.
Bandyopadhyay, A. K., Khattar, R., Puga, J., Fehlner, T. P. and Rheingold, A. L. (1992) Boron in new environments. Structure and reaction properties of discrete, mixed-metal, hexanuclear borides, Inorg. Chem. 31, 465.
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Fehlner, T.P. (1995). Cluster Equilibria. Relevance to the Energetics and Reactivity of Surface Bound Fragments. In: Farrugia, L.J. (eds) The Synergy Between Dynamics and Reactivity at Clusters and Surfaces. NATO ASI Series, vol 465. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-0133-2_6
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DOI: https://doi.org/10.1007/978-94-011-0133-2_6
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