Metal cluster systems

Sellers H 1991 On modeling chemisorption processes with metal cluster systems. II. Model atomic potentials and site specificity of N atom chemisorption on Pd(111) Chem. Phys. Lett. 178 351-7... 

A broader and more important implication of the oxychlorides is the potential of expanding the ligand combination to other transition-metal cluster systems. The advances in soft-chemistry techniques open up new possibilities for the sta-... 

Some general reviews on hydrogenation using transition metal complexes that have appeared within the last five years are listed (4-7), as well as general reviews on asymmetric hydrogenation (8-10) and some dealing specifically with chiral rhodium-phosphine catalysts (11-13). The topic of catalysis by supported transition metal complexes has also been well reviewed (6, 14-29), and reviews on molecular metal cluster systems, that include aspects of catalytic hydrogenations, have appeared (30-34). 

A search for alternative energy supplies has triggered efforts to develop efficient homogeneous catalysts for Fischer-Tropsch-type syntheses via hydrogenation of carbon monoxide, a likely future key material available, for example, through oxidation of coal (33, 327, 328, 417, 418). Metal cluster systems have been used in attempts to emulate the presently used heterogeneous catalysts. The important reactions are methanation,... 

The above observations strongly indicate that O-protonation is an important step in this particular reaction for the reduction of coordinated CO. Recent studies in our laboratory provide other examples of proton induced reduction in metal cluster systems, and an example of proton induced CO reduction has recently been reported by Atwood (44). It thus appears that protons as well as Lewis acids are effective in the bifunctional activation of coordinated CO. 

Information about internuclear distances in organic compounds has led to the view that the effective radius of an atom varies directly with bond order. This is understandable for elements like carbon, with a limited range of hybridized states, but less so for metallic (cluster) systems. The problem is threefold ... 

Thanks to the extensive literature on Aujj and the related smaller gold cluster compounds, plus some new results and reanalysis of older results to be presented here, it is now possible to paint a fairly consistent physical picture of the AU55 cluster system. To this end, the results of several microscopic techniques, such as Extended X-ray Absorption Fine Structure (EXAFS) [39,40,41], Mossbauer Effect Spectroscopy (MES) [24, 25, 42,43,44,45,46], Secondary Ion Mass Spectrometry (SIMS) [35, 36], Photoemission Spectroscopy (XPS and UPS) [47,48,49], nuclear magnetic resonance (NMR) [29, 50, 51], and electron spin resonance (ESR) [17, 52, 53, 54] will be combined with the results of several macroscopic techniques, such as Specific Heat (Cv) [25, 54, 55, 56,49], Differential Scanning Calorimetry (DSC) [57], Thermo-gravimetric Analysis (TGA) [58], UV-visible absorption spectroscopy [40, 57,17, 59, 60], AC and DC Electrical Conductivity [29,61,62, 63,30] and Magnetic Susceptibility [64, 53]. This is the first metal cluster system that has been subjected to such a comprehensive examination. 

J. C. Calabrese, L. F. Dahl, A. Cavalieri, P. Chini, G. Longoni, and S. Martinengo, Synthesis and Structure of a Hexanuclear Nickel Carbonyl Dianion, [Ni3(CO)3( j,2-CO)3]22, and Comparison with the [Pt3(CO)3(p2-CO)3]22 Dianion. An Unprecedented Case of a Metal Cluster System Possessing Different Metal Architectures for Congener Transition Metals, J. Am. Chem. Soc. 96, 2616-2618 (1974). 

Mixed metal clusters (clusters containing two different metals) have considerable potential for mechanistic studies. Three separate studies on iron mthenium clusters show the possibilities. Reactions of FeRu2(CO)i2 and Fe2Ru(CO)i2 in comparison to Fe3(CO)i2 and Ru3(CO)i2 show a very interesting activation of the iron center towards CO dissociation by ruthenium centers in the mixed metal-cluster system. Such an activation of the iron center by ruthenium has also been demonstrated for (/r-H)FeRu2(/(r-COMe)(CO)io. The presence of different metal centers for H2FeRu3(CO)i2 allowed unusually detailed interpretation of the isomerization, substitution, and CO exchange reactions. ... 

This is the first example of an abstraction reaction of a metal cluster system. ... 

Carbonyls.—A new type of metal cluster system has been synthesized, Nij(CO)g-( X4-PPh)6, which can be considered to be a metallic analogue of cubane, CgHg there is a cube of Ni atoms with each square Ni4 face symmetrically capped by a PPh ligand. 

Recent years there have been a considerable interest in studying of binary catalytic systems based on stabilized nanocomposites and amorphous alloys of copper with other metals. The reason is that the catalytic activity of such systems in many cases is sufficiently higher than that of individual metals. The most convenient model for theoretical description of binary systems characterized by the absence of far order is a cluster model. However, quantum-chemical study of binary clusters comprises the significantly more c omplicated problem than that o f individual metals, b ecause a correct theoretical description of metal-another metal cluster systems requires that the used method should be in a position to provide good results of calculations of geometrical, electron stmctures and energetic characteristics of both of individual metals. 

More recent developments in cluster chemistry have included the anchoring of clusters to silica or alumina surfaces via sol-gel processing, the products finding applications as catalyst precursors. Very recently, mixed-metal clusters have been incorporated onto the inner walls of mesoporous silica with a pore diameter of about 30 A, and have been subsequently converted into discrete nanoparticles by thermolysis, which have been shown to act as hydrogenation catalysts. This is a particularly important new use for mixed-metal cluster systems, since there are many well characterized mixed-metal cluster carbonyls vide infra) that are readily available to act as precursors for such reactions. 

Another area of major interest in the field is that of mixed metal cluster systems. Hieber very early in the study of metal carbonyl chemistry was able to prepare mercury complexes of the type Fe(CO)4(HgCl)2. The related gold ° compounds were prepared in the 1960s by reaction of phosphine gold halides with carbonyl anions. 

It is now clear that compounds with a wide range of nuclearity can be prepared but the difficulties in structure determination has restricted progress in the study of their chemistry. As mentioned above, these mixed clusters of high nuclearity are more or less at the present limits of the techniques available for structure determination. All work that has been carried out indicates that these compounds have a rich chemistry that is different from that of the smaller nuclearity metal cluster systems that have been the main concern to date. 

Several metal cluster systems have now been tried in the hydro-formylation reaction of propylene and CO + H2O (13), and as is seen from the data in Table I, some of them are found to be much superior to Fe(CO)5 as catalysts. This is especially true of Rh6(CO)ie and Ir4(CO)i2. 

A new type of electron-deficient metal cluster system, e.g. (61) and (62), has been identified by X-ray crystallography following the preparation of these compounds from [(t -Cp)2MoH2] and an excess of AljMe in toluene. Their ease of formation suggests that a considerable range of electron-deficient transition-metal compounds of this type should be isolable. ... 

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