Organometallic clusters precursors

Both PtRu/MgO catalysts prepared from cluster precursor and organometallic mixture were active for ethylene hydrogenation. The apparent activation energy of the former catalyst obtained from the Arrhenius plot during -40 to -25°C was 5.2 kcal/mol and that of the latter catalyst obtained during -50 to -30°C was 6.0 kcal/mol. The catalytic activity in terms of turn over frequency (TOP) was calculated on the assumption that all metal particles were accessible for reactant gas. Lower TOP of catalyst prepared from cluster A at -40°C, 57.3 x lO" s" was observed probably due to Pt-Ru contribution compared to that prepared from acac precursors. 

The first syntheses of organometallic clusters relied almost entirely upon serendipity, and even now designed syntheses of clusters of a desired metal composition are rarely achieved from lower nuclearity precursors. The basis for most syntheses involves ligand substitution of a hydrocarbon for a carbonyl ligand of a cluster having the desired metal composition, and then modification of the hydrocarbon unit while maintaining unchanged the metal-cluster core. ... 

Biomimetic Synthesis of Nanoparticles Carbonyl Complexes of the Transition Metals Metallic Materials Deposition Metal-organic Precursors Polynuclear Organometallic Cluster Complexes Porous Inorganic Materials Self-assembled Inorganic Architectures Semiconductor Nanocrystal Quantum Dots Sol-Gel Encapsulation of Metal and Semiconductor Nanocrystals. 

Through the years 1970-1990, most applications of organometallic clusters concerned catalysis, either as homogeneous catalysts or as precursors for heterogeneous catalysts. Since these two applications have been extensively reviewed and since homogeneous catalysis is treated elsewhere, the stricter definition of a metal cluster was used a... 

The nanostructures synthesis from organometallic unstable precursors can occur under controlled conditions. As a result, the nanoparticles have been specified by size, its distribution, stoichiometry and shape. The choice of organometallic compounds ligands can not only define the character of resulting cationic complex inorganic phases, the morphology of future nanoparticles (spheres, rods, cubes, wires), but can also affect their self-organization in one-, two-and three-dimensional clusters [338]. This approach is fruitful for the synthesis of nanoparticles of metals and alloys, simple and multication oxides and other compounds that exhibit ferroic properties. 

Metal clusters on supports are typically synthesized from organometallic precursors and often from metal carbonyls, as follows (1) The precursor metal cluster may be deposited onto a support surface from solution or (2) a mononuclear metal complex may react with the support to form an adsorbed metal complex that is treated to convert it into an adsorbed metal carbonyl cluster or (3) a mononuclear metal complex precursor may react with the support in a single reaction to form a metal carbonyl cluster bonded to the support. In a subsequent synthesis step, metal carbonyl clusters on a support may be treated to remove the carbonyl ligands, because these occupy bonding positions that limit the catalytic activity. 

The field of surface-mediated synthesis of metal carbonyl clusters has developed briskly in recent years [4-6], although many organometallic chemists still seem to be unfamiliar with the methods or consider themselves ill-equipped to carry them out. In a typical synthesis, a metal salt or an organometallic precursor is brought from solution or the gas phase onto a high-area porous metal oxide, and then gas-phase reactants are brought in contact with the sample to cause conversion of the surface species into the desired products. In these syntheses, characteristics such as the acid-base properties of the support influence fhe chemisfry, much as a solvenf or coreactant influences fhe chemisfry in a convenfional synfhesis. An advanfage of... 

Perrhenate and related building blocks are constituents of several cluster compounds where they act as terminal groups in organometallic rhenium oxides such as in [(cp Re)3(//2-0)3(/U3-0)3Re03]+ (49)21 Qj. jjj heterometallic clusters such as the structurally related [(Re)3(//f dppm)3(/u -0)3Re03]+ (dppm = bis(diphenylphosphino)methane) and Pt4 P(C6H 11)3)4 (//-C0)2(Re04)2]. A series of platinum-rhenium and platinum-rhenium-mercury clusters with Pt-Re multiple bonds has been isolated from reactions of Pt3 precursors with Rc207 or perrhenate. " ... 

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