Catalysis cluster formation

The sonochemistry of solutes dissolved in organic Hquids also remains largely unexplored. The sonochemistry of metal carbonyl compounds is an exception (57). Detailed studies of these systems led to important mechanistic understandings of the nature of sonochemistry. A variety of unusual reactivity patterns have been observed during ultrasonic irradiation, including multiple ligand dissociation, novel metal cluster formation, and the initiation of homogeneous catalysis at low ambient temperature (57). 

Laine and co-workers have studied the mechanism involved in rhodium-catalysed benzaldehyde hydrogenation, using [Rh6(CO)i6] as catalyst precursor. Following kinetic arguments, the authors proposed cluster catalysis with a limiting step corresponding to the break of metal-metal bond and/or isomerisation of the cluster formation [22]. 

One of the limitations of both 4 and 7 in catalysis is their ready decomposition to inactive cluster hydride complexes in the absence of substrate. If the substrate is a weak ligand (e.g., Me2C=CMe2), this decomposition can be competitive with cluster formation. A high concentration of substrate favors catalysis... 

The MO calculations explain a possible route for silver cluster formation and catalysis in silver bromide. The electron affinity of the silver center determines... 

For more than two decades, extensive research work has been devoted to the unique properties of clusters. They are made of a small number (or nucleaiity) of atoms or molecules only, and therefore constitute a new state of matter, or mesoscopic phase, between the atom or molecule and the crystal. New methods have been developed in physics and chemistry for their synthesis, their direct observation, the study of their properties, and of their crucial role in number of processes, such as phase transition, catalysis, surface phenomena, imaging. Owii to its specific approach, radiation chemistry offei first the opportunity to reveal the existence of nuclearity-dependent properties of clusters and has then proven to be a powerfid method to study the mechanisms of cluster formation and reactivity in solution. 

Boyington JC, VN Gladyshev, SV Khangulov, TC Stadtman, PD Sun (1997) Crystal structure of formate dehydrogenase H catalysis involving Mo, molybdopterin, selenocysteine, and an Fe4S4 cluster. Science 275 1305-1308. 

Fischer-Tropsch catalysis, 34 71, 38 331-335 C2 oxygenate formation, 38 338 oxide-supported osmium clusters, 38 335 product selectivites, 38 333-334 proton-induced reduction of CO, 38 332-333... 

---