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Rhodium dicarbonyl sites on alumina surfaces. 1. Preparation and characterization of a model system

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100406a016· OSTI ID:5456866

A high surface area alumina readily chemisorbs the Rh carbonyl compound Rh/sub 2/(CO)/sub 4/Cl/sub 2/ from alkane solvents at room temperature. Samples prepared in this manner containing ca. 1 wt % Rh have been characterized by transmission electron microscopy, transmission infrared spectroscopy, solid state /sup 13/C NMR with magic-angle spinning, and low-temperature ESR. The exchange of Rh-/sup 12/CO surface complexes with gas-phase /sup 13/CO has also been studied. These data indicate such preparations afford dispersed Al-O-Rh(CO)/sub 2/ surface complexes which form dative bonds with neighboring surface hydroxyl or oxo groups, but do not vibrationally or electronically interact with each other. In this way the Rh(CO)/sub 2/ species on this model system are viewed as truly isolated. A model is also proposed for the Rh(CO)/sub 2/ sites which form when alumina-supported Rh salts are reduced in H/sub 2/ and then exposed to CO. By this model those materials also contain roughly square-planar Al-O-Rh(CO)/sub 2/ species, but here they are clustered in aggregates near a minority of paramagnetic Rh sites. The latter serve to enhance the relaxation rates of /sup 13/CO coordinated to the diamagnetic Rh/sup 1 +/ sites in NMR experiments.

Research Organization:
Exxon Corporate Research Science Labs., Annandale, NJ
OSTI ID:
5456866
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:15; ISSN JPCHA
Country of Publication:
United States
Language:
English