On ruthenium

A typical SSIMS spectrum of an organic molecule adsorbed on a surface is that of thiophene on ruthenium at 95 K, shown in Eig. 3.14 (from the study of Cocco and Tatarchuk [3.28]). Exposure was 0.5 Langmuir only (i.e. 5 x 10 torr s = 37 Pa s), and the principal positive ion peaks are those from ruthenium, consisting of a series of seven isotopic peaks around 102 amu. Ruthenium-thiophene complex fragments are, however, found at ca. 186 and 160 amu each has the same complicated isotopic pattern, indicating that interaction between the metal and the thiophene occurred even at 95 K. In addition, thiophene and protonated thiophene peaks are observed at 84 and 85 amu, respectively, with the implication that no dissociation of the thiophene had occurred. The smaller masses are those of hydrocarbon fragments of different chain length. 

SSIMS has also been used to study the adsorption of propene on ruthenium [3.29], the decomposition of ammonia on silicon [3.30], and the decomposition of methane thiol on nickel [3.31]. 

For ruthenium, electrolytes based on ruthenium sulphamate or nitrosyl-sulphamate have been described, but the most useful solutions currently available are based on the anionic complex (H2 0 Cl4 Ru N Ru-Cl4-OH2) . The latter solutions operate with relatively high cathode efficiency to furnish bright deposits up to a thickness of about 0-005 0 mm, which are similar in physical characteristics to electrodeposited rhodium and have shown promise in applications for which the latter more costly metal is commonly employed. Particularly interesting is the potential application of ruthenium as an alternative to gold or rhodium plating on the contact members of sealed-reed relay switches. 

Structural data on ruthenium porphyrins shows that the Ru-N (porphyrin) distance is relatively unaffected by changing the oxidation state, as expected for a metal atom inside a fairly rigid macrocyclic ring (Table 1.11). 

In contrast to the situation with copper-based catalysis, most studies on ruthenium-based catalysts have made use of preformed metal complexes. The first reports of ruthenium-mediated polymerization by Sawamoto and coworkers appeared in I995.26 In the early work, the square pyramidal ruthenium (II) halide 146 was used in combination with a cocatalyst (usually aluminum isopropoxide). 

Gallezot, P., Nicolaus, N., Fleche, G., Fuertes, P., and Perrard, A. (1998) Glucose hydrogenation on ruthenium catalysts in a trickle-bed reactor. J. 

Systems like SFg [39, 40], HjO [41], CH3OH [41], and CBr4/C6Hi2 [42] have been examined using this technique. Three recent papers on ruthenium (11) tris-2, 2 -bipyridine, or [Ru (bpy)3] " [43], on photosynthetic O2 formation in biological systems [44], and on photoexcitation of NITPP — L2 [45] in solution also merit attention. Theoretical work advanced at the same time. Early approaches are due to Wilson et al. [46], whereas a statistical theory of time-resolved X-ray absorption was proposed by Mukamel et al. [47, 48]. This latter theory represents the counterpart of the X-ray diffraction theory developed in this chapter. 

Ozenler SS, Kadirgan F (2006) The effect of the matrix on the electro-catalytic properties of methanol tolerant oxygen reduction catalysts based on ruthenium-chalcogenides. J Power Sources 154 364-369... 

Similar structural changes of the copper layer on ruthenium are observed for the ethane hydrogenolysls reaction shown In Figure 10 (12). The effect of copper at low coverages Is to simply block active ruthenium sites on a one to one basis with three dimensional cluster growth occurring at roughly a third of a monolayer. 

This discussion of EXAFS on ruthenium-copper clusters has emphasized qualitative aspects of the data analysis. A quantitative data analysis, yielding information on the various structural parameters of interest, has also been made and published (8). Of particular Interest was the finding that the average compo tion of the first coordination shell of ruthenium and copper atoms about a ruthenium atom was about 90% ruthenium, while that about a copper atom was about 50% ruthenium. Details of the methods Involved in the quantitative analysis of EXAFS data on bimetallic clusters can be obtained from our original papers (8.12-15). 

The ruthenium-copper and osmium-copper systems represent extreme cases in view of the very limited miscibility of either ruthenium or osmium with copper. It may also be noted that the crystal structure of ruthenium or osmium is different from that of copper, the former metals possessing the hep structure and the latter the fee structure. A system which is less extreme in these respects is the rhodium-copper system, since the components both possess the face centered cubic structure and also exhibit at least some miscibility at conditions of interest in catalysis. Recent EXAFS results from our group on rhodium-copper clusters (14) are similar to the earlier results on ruthenium-copper ( ) and osmium-copper (12) clusters, in that the rhodium atoms are coordinated predominantly to other rhodium atoms while the copper atoms are coordinated extensively to both copper and rhodium atoms. Also, we conclude that the copper concentrates in the surface of rhodium-copper clusters, as in the case of the ruthenium-copper and osmium-copper clusters. 

Role of adsorbed hydrogen species on ruthenium and molybdenum sulfides. Characterization by inelastic neutron scattering, thermoanalysis methods and model reactions. 

The coordination of ligands at the surface of metal nanoparticles has to influence the reactivity of these particles. However, only a few examples of asymmetric heterogeneous catalysis have been reported, the most popular ones using a platinum cinchonidine system [65,66]. In order to demonstrate the directing effect of asymmetric ligands, we have studied their coordination on ruthenium, palladium, and platinum nanoparticles and the influence of their presence on selected catalytic transformations. 

Goodman DW, Peden CHF, Chen MS. 2007. CO oxidation on ruthenium The nature of the active catal3dic surface. Surf Sci 601 L124. 

P. Gallezot, N. Nicolaus, G. Fleche, P. Fuertes and A. Perrard, Glucose Hydrogenation on Ruthenium Catalysts in a Trickle-Bed Reactor, Journal of Catalysis 180 (1998) 51. 

The nitrogen on ruthenium work is consistent with the observation made on the H/Cl/Au Eley-Rideal chemistry and, taken together, the implications of these two pieces of work are quite profound, suggesting that an accurate theory of surface reactions cannot be constructed without accounting for strong coupling between the reaction coordinate and the metals electron... 

Synthesis and characterization of a new class of anti-angiogenic agents based on ruthenium clusters... 

How to cite this article Nazarov, A. A. et al. Synthesis and characterization of a new class of anti-angiogenic agents based on ruthenium clusters. Sci. Rep. 3, 1485 DOL10.1038/ srep01485 (2013). 

The main reason for the rapid development of metathesis reactions on a laboratory scale (the reaction itself had been known for quite a long time) has been the development of active and robust second-generation ruthenium catalysts (6/3-14 to 6/3-16), which usually provide better yields than the first-generation Grubbs catalysts (6/3-9 or 6/3-13) (Scheme 6/3.2). This also reflects the huge number of domino processes based on ruthenium-catalyzed metathesis, which is usually followed by a second or even a third metathesis reaction. However, examples also exist where, after a metathesis, a second transition metal-catalyzed transformation or a pericyclic reaction takes place. 

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