Ruthenium, as catalyst

Hydrogenation of aldoses to alditols (polyhydric alcohols) is usually performed in an aqueous solution with nickel or ruthenium as catalyst, as seen in the examples shown in eqs. 5.9-5.11.17-19... 

Ruthenium was recognized early to be the catalyst which produced the largest amount of the intermediate cyclohexene from the xylenes, rhodium and platinum giving decreasing amounts. The importance of water in maximizing the yield of cyclohexene using ruthenium as catalyst was demonstrated by Don and Scholten." A recent patent application claims yields of 48% cyclohexene at 60% conversion of the benzene. ... 

The Action of Rhodium and Ruthenium as Catalysts for Liquid-Phase Hydrogenation... 

But these syntheses, together with that from carbon monoxide and hydrogen at temperatures of around 140°C and pressures above 500 bar with ruthenium as catalyst, have no commercial significance, which is in contrast to syntheses from ethylene. 

This model raises the issue of the effective thickness of the electrochemically active portion of the anode structure. Primdahl and Mogensen [20] found no correlation between polarisation effects and electrode thickness down to 20 pm, and in more recent work [26] a depth of 10 pm for the active zone is sustained. Mathematical modelling [29] is in accord with this experimental evidence (Figure 6.11). Beyond that thickness, the cermet can be regarded as a passive contact layer, and in anode-supported intermediate temperature fuel cells, as also having a structural and mechanical function. It is therefore available as a site for fuel reactions such as reforming. Some studies with this as objective have already been reported, such as the incorporation of ruthenium as catalyst [30],... 

Ruthenium. Ruthenium, as a hydroformylation catalyst (14), has an activity signiftcandy lower than that of rhodium and even cobalt (22). Monomeric mthenium carbonyl triphenylphosphine species (23) yield only modest normal to branched regioselectivities under relatively forcing conditions. For example, after 22 hours at 120°C, 10 MPa (1450 psi) of carbon monoxide and hydrogen, biscarbonyltristriphenylphosphine mthenium [61647-76-5] ... 

As catalysts, ruthenium- or molybdenum-alkylidene complexes are often employed, e.g. commercially available compounds of type 7. Various catalysts have been developed for special applications. " ... 

Hydrogenation of olefinic unsaturation using ruthenium (Ru) catalyst is well known. It has been widely used for NBR hydrogenation. Various complexes of Ru has been developed as a practical alternative of Rh complexes since the cost of Ru is one-thirtieth of Rh. However, they are slightly inferior in activity and selectivity when compared with Rh catalyst. 

High-valent ruthenium oxides (e. g., Ru04) are powerful oxidants and react readily with olefins, mostly resulting in cleavage of the double bond [132]. If reactions are performed with very short reaction times (0.5 min.) at 0 °C it is possible to control the reactivity better and thereby to obtain ds-diols. On the other hand, the use of less reactive, low-valent ruthenium complexes in combination with various terminal oxidants for the preparation of epoxides from simple olefins has been described [133]. In the more successful earlier cases, ruthenium porphyrins were used as catalysts, especially in combination with N-oxides as terminal oxidants [134, 135, 136]. Two examples are shown in Scheme 6.20, terminal olefins being oxidized in the presence of catalytic amounts of Ru-porphyrins 25 and 26 with the sterically hindered 2,6-dichloropyridine N-oxide (2,6-DCPNO) as oxidant. The use... 

Fuel cells essentially reverse the electrolytic process. Two separated platinum electrodes immersed in an electrolyte generate a voltage when hydrogen is passed over one and oxygen over the other (forming H30+ and OH-, respectively). Ruthenium complexes are used as catalysts for the electrolytic breakdown of water using solar energy (section 1.8.1). 

Transition metal catalysts arc characterized by their redox ehemistry (catalysts can be considered as one electron oxidants/reductants). They may also be categorized by their halogen affinity. While in the initial reports on ATRP (and in most subsequent work) copper266,267 or ruthenium complexes267 were used, a wide range of transition metal complexes have been used as catalysts in ATRP. 

The metathesis of ene-ynamides has been investigated by Mori et al. and Hsung et al. [80]. Second-generation ruthenium catalysts and elevated temperatures were required to obtain preparatively useful yields. Witulski et al. published a highly regioselective cyclotrimerization of 1,6-diynes such as 98 and terminal alkynes using the first-generation ruthenium metathesis catalyst 9... 

Transition-metal-based Lewis acids such as molybdenum and tungsten nitro-syl complexes have been found to be active catalysts [49]. The ruthenium-based catalyst 50 (Figure 3.6) is very effective for cycloadditions with aldehyde- and ketone-bearing dienophiles but is ineffective for a,)S-unsaturated esters [50]. It can be handled without special precautions since it is stable in air, does not require dry solvents and does not cause polymerization of the substrates. Nitromethane was the most convenient organic solvent the reaction can also be carried out in water. 

Kiindig EP, Saudan CM, Viton F (2001) Chiral cyclopentadienyl-iron and -ruthenium Lewis acids containing the electron-poor BIPHOP-F ligand a comparison as catalysts in an asymmetric Diels-Alder reaction. Adv Synth Catal 343 51-56... 

Many late transition metals such as Pd, Pt, Ru, Rh, and Ir can be used as catalysts for steam reforming, but nickel-based catalysts are, economically, the most feasible. More reactive metals such as iron and cobalt are in principle active but they oxidize easily under process conditions. Ruthenium, rhodium and other noble metals are more active than nickel, but are less attractive due to their costs. A typical catalyst consists of relatively large Ni particles dispersed on an AI2O3 or an AlMg04 spinel. The active metal area is relatively low, of the order of only a few m g . ... 

The copper EXAFS of the ruthenium-copper clusters might be expected to differ substantially from the copper EXAFS of a copper on silica catalyst, since the copper atoms have very different environments. This expectation is indeed borne out by experiment, as shown in Figure 2 by the plots of the function K x(K) vs. K at 100 K for the extended fine structure beyond the copper K edge for the ruthenium-copper catalyst and a copper on silica reference catalyst ( ). The difference is also evident from the Fourier transforms and first coordination shell inverse transforms in the middle and right-hand sections of Figure 2. The inverse transforms were taken over the range of distances 1.7 to 3.1A to isolate the contribution to EXAFS arising from the first coordination shell of metal atoms about a copper absorber atom. This shell consists of copper atoms alone in the copper catalyst and of both copper and ruthenium atoms in the ruthenium-copper catalyst. 

Since ruthenium and rhodium are neighboring elements in the periodic table, a closer comparison of the properties of ruthenium-copper and rhodium-copper clusters is of interest (17). When we compare EXAFS results on rhodium-copper and ruthenium-copper catalysts in which the Cu/Rh and Cu/Ru atomic ratios are both equal to one, we find some differences which can be related to the differences in miscibility of copper with ruthenium and rhodium. The extent of concentration of copper at the surface appears to be lower for the rhodium-copper clusters than for the ruthenium-copper clusters, as evidenced by the fact that rhodium exhibits a greater tendency than ruthenium to be coordinated to copper atoms in such clusters. The rhodium-copper clusters presumably contain some of the copper atoms in the interior of the clusters. 

For the last 2 decades ruthenium carbene complexes (Grubbs catalyst first generation 109 or second generation 110, Fig. 5.1) have been largely employed and studied in metathesis type reactions (see Chapter 3) [31]. However, in recent years, the benefits of NHC-Ru complexes as catalysts (or pre-catalysts) have expanded to the area of non-metathetical transformations such as cycloisomerisation. 

WO 2009/124853 Al, F Hoffmann-La Roche AG New ruthenium complexes as catalysts for metathesis reactions... 

The choice of the metals is strictly related to the catalytic application. As we shall show later, the catal54ic reaction most commonly investigated with polymer supported M / CFP catalysts is hydrogenation (Table 3). The overwhelming majority of catalytic studies concerns the hydrogenation of alkenes and by far the most commonly employed metal is palladium, followed by platinum. Examples of rhodium and ruthenium hydrogenation catalysts supported on pol5uneric supports are very rare. 

In 2005, Nguyen et al. reported the first example of asymmetric cyclopropa-nation of olefins with EDA mediated by a combination of a (salen) ruthenium(II) catalyst and a catalytic amount of a chiral sulfoxide (Scheme 6.7). These authors proposed that the mechanism explaining the asymmetric induction involved the axial coordination of the chiral sulfoxide to the ruthenium centre as the key induction step in the reaction stereoselectivity. 

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