Bimetallic cluster compounds

A brief overview of bimetallic catalysts is presented. Electronic vs. ensemble effects are discussed, and literature is reviewed on single crystal bimetallics, and supported bimetallic clusters. Bimetallic cluster compounds are considered as models. Structural considerations, effects of potential poisons, particles from bimetallic cluster compounds, and catalytic activity/selectivity studies are briefly reviewed and discussed. 

A few illustrative examples dealing with bimetallic cluster compounds will now be presented. For example, mixed cluster compounds [MjRu -CO CO qCPPI J where M = Cu, Ag, and Au have been prepared and structurally characterized. ) Metal core structures consist of a Ru4 tetrahedron with M-PPh3 groups capping two... 

Heterogeneous Catalysts Derived from Bimetallic Cluster Compounds... 

Supported mixed metal catalysts are also prepared by other means such as the deposition of bimetallic colloids onto a support O and the decomposition of supported bimetallic cluster compounds.208 The photocatalytic codeposition of metals onto titania was also attempted with mixed results.209 with a mixture of chloroplatinic acid and rhodium chloride, very little rhodium was deposited on the titania. With aqueous solutions of silver nitrate and rhodium chloride, more rhodium was deposited but deposition was not complete. In aqueous ammonia, though, deposition of both silver and rhodium was complete but the titania surface was covered with small rhodium crystallites and larger silver particles containing some rhodium. With a mixture of chloroplatinic acid and palladium nitrate both metals were deposited but, while most of the resulting crystallites were bimetallic, the composition varied from particle to particle.209... 

Bimetallic cluster compounds containing coinage metals and peripheral Fe(CO)4 groups have been synthesized and show a considerable structural variety. Particularly interesting are the clusters of composition [M4 Fe(CO)4 4]" (M = Ag, Au). Clusters of other stoichiometry have been isolated with M = The metal... 

The subject of heteronuclear cluster compounds of the transition metals remains an active area of research interest, and was reviewed in the early 1980s by Geoffroy el al. (1,2). Clusters with novel architectures, exemplified by the star clusters of Stone and co-workers (5), continue to be synthesized. Whereas there is undoubtedly strong academic interest in the structure, bonding, and chemical reactivity of heteronuclear clusters in their own right, additional impetus to this field is given by the important relationship between heteronuclear clusters and bimetallic alloy catalysts. This relationship was the subject of a published symposium (4). 

Iron-only hydrogenase, dithiolate-bridged compounds as biomimetic models, 6, 239 Iron oxide films, synthesis, 12, 51 Iron-palladium nanoparticles, preparation, 12, 74 Iron-platinum bimetallic clusters, with isocyanide clustes,... 

The cluster compounds (RCN)2M2Ru6C(CO)16 where R=C1-C6 alkyl, Ph, or 6 C 0 aralkyl, and M = Cu, Ag, or Au, are useful bimetallic systems for converting CO + H2 to CH3OH.(74) No catalyst support was employed, and a static reactor operating at 275 °C at moderate pressures was effective (no hydrocarbons were produced). 

Supported bimetallic catalysts can be made by adsorption of a bimetallic precursor such as molecular cluster compounds, colloidal particles or dendrimer-stabilised particles. In several cases, homogeneous bimetallic particles have been found where the compositions lie within the miscibility gap of the bulk alloy (e.g. with PtAu particles). This suggests that when the particles are small enough and do not possess metallic properties, the normal rules do not apply. 

Bimetallic molecular cluster compounds containing gold will adsorb intact on supports, and the ligands may then be removed by heating, but only a few such compounds are available. Simple carbonyl complexes do not exist,... 

Fig. 23. Correlation between rates of product formation in the CO + Hj reaction and Ir/Fe atomic ratios of catalysts prepared from Si02-supported IrFe bimetallic carbonyl cluster compounds.

A variety of metal cluster compounds have been chemically bound on amorphous metal oxides and entrapped inside zeolite cages by new preparative tools such as surface organometallic chemistry and the so-called ship-in-bottle technique. They oflier much promise as molecular precursors for rational preparation of tailored metal catalysts having a uniform distribution of discrete metal-bimetallic ensembles, namely, organometallics which are active for catalytic reactions. They also provide advantages as metal precursors to achieve higher metal dispersions and well-managed metal... 

The selective production of methanol and of ethanol by carbon monoxide hydrogenation involving pyrolysed rhodium carbonyl clusters supported on basic or amphoteric oxides, respectively, has been discussed. The nature of the support clearly plays the major role in influencing the ratio of oxygenated products to hydrocarbon products, whereas the nuclearity and charge of the starting rhodium cluster compound are of minor importance. Ichikawa has now extended this work to a study of (CO 4- Hj) reactions in the presence of alkenes and to reactions over catalysts derived from platinum and iridium clusters. Rhodium, bimetallic Rh-Co, and cobalt carbonyl clusters supported on zinc oxide and other basic oxides are active catalysts for the hydro-formylation of ethene and propene at one atm and 90-180°C. Various rhodium carbonyl cluster precursors have been used catalytic activities at about 160vary in the order Rh4(CO)i2 > Rh6(CO)ig > [Rh7(CO)i6] >... 

---