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Metal-hydrogen bridge bonding of hydrocarbons on metal surfaces
R M Gavin1, J Reutt, E L Muetterties
1Department of Chemistry, Haverford College, Haverford, Pennsylvania 19041.
Abstract:
Molecular orbital studies implicate multicenter metal-hydrogen-carbon interactions as contributors to the bonding of chemisorbed hydrocarbons on clean metal surfaces. The most stable geometries appear to be those that achieve the maximum multicenter bonding to the coordinately unsaturated metal atoms in the vicinity of the anchoring metal-carbon interaction. Energy differences between possible surface sites are of the same magnitude as stabilization energies for three-center bonding of hydrogen atoms to the metal surface. Accordingly, secondary interactions of hydrogen with neighboring metal atoms may be significant determining factors in surface structures. The model predictions are compared with known structures and are used to propose a mechanism for hydrocarbon reactions on metal surfaces. These metal-hydrogen-carbon interactions are presumed to be intermediate points or states in C-H bond-breaking processes.
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