Abstract
Metal clusters present an exciting challenge in structure, bonding, theory, chemistry and reaction mechanism. One intriguing possibility in clusters is their emulation, on a localized basis, of metal surfaces with chemisorbed species.3,4 some instances, these metal clusters may be better models of surfaces with chemical sorbed species than mononuclear metal complexes.3–5 D We describe here the results of an extensive literature 5,6 analysis of the cluster-surface analogy and experimental studies of polynuclear rhodium hydrides which present a simple model of catalytic hydrogenation of olefins on a metal surface.
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Paper 21 in this series. R. K. Brown, J. W. Williams, M. F. Fredrich and V. W. Day, Proc. Natl. Acad. Sci. 76, 0000 (1979).
To whom correspondence should be addressed. Present address: Department of Chemistry, University of California, Berkeley, CA 94720.
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An alternative strategy that can successfully circumvent the proclivity of some clusters to fragment is use of a cluster that has one or more very weakly bound ligands that through facile dissociation processes can generate the requisite sites for substrate binding in catalytic cycles.
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Here again fragmentation of a cluster may occur if the metal aggregate is weakly held together or if the largely M-M bonding orbitals are substantially affected in the generation of additional M-L ligand bonding orbitals in any part of the reaction cycle.
Ligand or substrate binding may substantially weaken the metal-metal bonds at a metallic surface. Although an unzipping process to yield molecular species cannot occur for these surface atoms unless26 a volatile species, e. g., a metal carbonyl, is formed, there may be a surface (metal atom) reconstruction following or concurrent with the actual chemisorption process. Individual metal atoms at a surface are not rigidly fixed. Scission of metal-metal bonds can occur.
Of course, reactants like oxygen, sulfur and halogens can generate non-metallic surfaces such as oxides, sulfides and halides whereby there is no essential metal-metal bonding extant in the outer surface layers.
E. L. Muetterties, Boron Hydride Chemistry, Academic Press, New York, 1975, pp. 1–3.
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Muetterties, E.L., Sivak, A.J., Brown, R.K., Williams, J.W., Fredrich, M.F., Day, V.W. (1979). Metal Clusters 22 The Polynuclear Rhodium Hydride Set {HRhL2}n . In: Tsutsui, M. (eds) Fundamental Research in Homogeneous Catalysis. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-2958-9_33
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