MgO-supported bimetallic catalysts consisting of segregated, essentially molecular rhodium and osmium species.

A family of supported bimetallic samples was prepared by the reactions of Rh(C2H4)(acac) (acac = acetylacetonate) and Os3(CO)12 with MgO. The samples were characterized by infrared and extended X-ray absorption fine structure spectroscopies, before and after various treatments with hydrogen at temperatures up to 393 K. The spectra identify the following combinations of supported species: (a) [Os3(CO)11](2-) + Rh(C2H4)2, (b) [Os3(CO)11](2-) + Rh(CO)2, and (c) [Os3(CO)11](2-) + rhodium clusters containing approximately 4 to 6 atoms each, on average. No bimetallic clusters formed. The triosmium frame remained intact while the rhodium surface species were reduced in the presence of H2. The samples were tested as catalysts for ethylene hydrogenation at 298 K, and the catalytic activity matched that of the rhodium complexes alone; evidently the rhodium complexes were responsible for all the catalysis, with the osmium clusters remaining inactive because of the presence of the carbonyl ligands on them.