Ruthenium 382 Subject

Ruthenium and Os are stable to atmospheric attack though if Os is very finely divided it gives off the characteristic smell of OSO4. By contrast, iron is subject to corrosion in the form of rusting which, because of its great economic importance, has received much attention (see Panel above). 

ESR spectra were recorded on a JEOL JES-RE2X spectrometer. About 250 mg of ruthenium-free titanate samples was subjected to heat treatment either in vacuum at 573 K or in a hydrogen atmosphere at 973 K. For measurements of ESR spectra, 30 Torr of O2 or N2O was introduced at room temperature and then cooled to 77 K without evacuation. The spectra were obtained in the dark and under UV irradiation with a 500 W low pressure mercury lamp. 

In 2009, Buchmeiser and co-workers reported the synthesis of a novel ruthenium complex 54 based on a seven-membered NHC ligand [68] (Fig. 3.22). To examine the catalytic activity of complex 54 in the RCM reaction, the authors subjected the complex to a series of typical RCM reactions by using substrates 1, 3, and 5. Pre-catalyst 54 showed only moderate reactivity with 1 and 3 and no reaction occurred with 5. 

Carbon-supported Ru-Sn catalyst Ru and Sn Mossbauer measurements were performed to investigate catalysts of ruthenium and tin supported on activated carbon (Ru-Sn/C). The samples were subjected to different reducing and oxidizing treatments. The presence of tin leads to a substantial increase of the Lamb-Mossbauer factor of the metallic Ru-particles showing that tin strengthens the attachment of the particles to the support. The close contact between the two metals appears to be decisive for the formation of catalytically active sites (Ru-Sn and Ru-SnOj,-)... 

The most widely used method for adding the elements of hydrogen to carbon-carbon double bonds is catalytic hydrogenation. Except for very sterically hindered alkenes, this reaction usually proceeds rapidly and cleanly. The most common catalysts are various forms of transition metals, particularly platinum, palladium, rhodium, ruthenium, and nickel. Both the metals as finely dispersed solids or adsorbed on inert supports such as carbon or alumina (heterogeneous catalysts) and certain soluble complexes of these metals (homogeneous catalysts) exhibit catalytic activity. Depending upon conditions and catalyst, other functional groups are also subject to reduction under these conditions. 

Precious metals reclamation Precious metals reclamation is the recycling and recovery of precious metals (i.e., gold, silver, platinum, palladium, iridium, osmium, rhodium, and ruthenium) from hazardous waste. Because U.S. EPA found that these materials will be handled protectively as valuable commodities with significant economic value, generators, transporters, and storers of such recyclable materials are subject to reduced requirements. 

Fig. 3. Vibrational population distributions of N2 formed in associative desorption of N-atoms from ruthenium, (a) Predictions of a classical trajectory based theory adhering to the Born-Oppenheimer approximation, (b) Predictions of a molecular dynamics with electron friction theory taking into account interactions of the reacting molecule with the electron bath, (c) Born—Oppenheimer potential energy surface, (d) Experimentally-observed distribution. The qualitative failure of the electronically adiabatic approach provides some of the best available evidence that chemical reactions at metal surfaces are subject to strong electronically nonadiabatic influences. (See Refs. 44 and 45.)...

Since Chatt and Davidson13 observed the first clear example of simple oxidative addition of a C—H bond of naphthalene to a ruthenium metal center, Ru(dmpe)2 (dmpe = Me2PCH2CH2PMe2), hydrocarbon activation has been the subject of many transition metal studies.11 c Sometimes, the efforts in this field have ended in findings different from the initial objectives, which have been the starting point for the development of novel organometallic chemistry. 

The potential of ECL in analytical chemistry has only more recently been investigated, but has rapidly gained recognition as both a sensitive and selective method of detection. Most reported applications have utilized the tris(2,2 -bipyri-dyl) ruthenium(II) [Ru(bpy)32+] ECL reaction, or else the electrochemical initiation of more conventional CL reactions, but many other potentially useful systems have been investigated. The applications of ECL in analytical chemistry have recently been the subject of comprehensive reviews [12-16],... 

Representatives of the bridged sulfone system 70 have been subjected to ruthenium catalysed ring-closing metathesis reactions (Grubbs catalyst) and shown to afford, in low yields, a few selected cyclic dimers and trimers, of all the possibilities available. The diastereoselectivities observed were rationalised in terms of kinetic control involved with internal ruthenium/sulfonyl oxygen coordination . 

This excellent regiocontrol was exploited by subjecting terminal alkenes and hydroxyalkynoates to ruthenium catalysis conditions to afford butenolides and pentenolides (Equation (23)).36 The Alder-ene reaction occurs preferentially to form the G-G bond at the alpha-carbon of the alkynoate. The unusually high regioselectivity is attributed to a synergistic effect derived from an enhanced coordination of the hydroxyl group to the ruthenium. 

The conversion of iron catalysts into iron carbide under Fischer-Tropsch conditions is well known and has been the subject of several studies [20-23], A fundamentally intriguing question is why the active iron Fischer-Tropsch catalyst consists of iron carbide, while cobalt, nickel and ruthenium are active as a metal. Figure 5.9 (left) shows how metallic iron particles convert to carbides in a mixture of CO and H2 at 515 K. After 0.5 and 1.1 h of reaction, the sharp six-line pattern of metallic iron is still clearly visible in addition to the complicated carbide spectra, but after 2.5 h the metallic iron has disappeared. At short reaction times, a rather broad spectral component appears - better visible in carburization experiments at lower temperatures - indicated as FexC. The eventually remaining pattern can be understood as the combination of two different carbides -Fe2.2C and %-Fe5C2. 

Tab. 8.1 summarizes the various substrates that were subjected to the rhodium-catalyzed reaction using a Rh-dppb catalyst system. Only ds-alkenes were cycloisomerized under these conditions, because the trans-alkenes simply did not react. Moreover, the formation of the y-butyrolactone (Tab. 8.1, entry 8) is significant, because the corresponding palladium-, ruthenium-, and titanium-catalyzed Alder-ene versions of this reaction have not been reported. In each of the precursors shown in Tab. 8.1 (excluding entry 7), a methyl group is attached to the alkene. This leads to cycloisomerization products possessing a terminal alkene, thus avoiding any stereochemical issues. Also,... 

The treatment of this insoluble residue may vary. In one typical process, residue is subjected to fusion with sodium peroxide. Ruthenium and osmium are converted to water-soluble sodium ruthenate and osmate, which are leached with water. The aqueous solution is treated with chlorine gas and heated. The ruthenate and the osmate are converted to their tetroxides. Ruthenium tetroxide is distilled out and collected in hydrochloric acid. The tetroxide is converted into ruthenium chloride. Traces of osmium are removed from ruthenium chloride solution by boiling with nitric acid. 

Only a few publications dealing with this subject can be found in the literature. Hydrogenation of diketo esters A with chirally modified ruthenium catalysts resulted in mixtures of syn- and anti-dihydroxy esters C with varying enantiomeric excesses [5], A notable exception to this is represented by the recent work of Car-pentier et al., who succeeded in controlling the reduction of methyl 3,5-dioxohex-anoate at the initial step, namely the reduction of the P-keto group. The enantiomeric excess achieved was, nevertheless, limited to 78% at best [5a]. 

For these reasons, and the relative ease with which the complexes are prepared, an increasing number of studies have been performed on the photophysical and photochemical properties of such complexes. Though most of the studies in this area have been performed on dinuclear ruthenium complexes, an increasing number of Ru/Os and Os/Os dimers have been studied in recent years (228, 541-552) and this subject has been reviewed (222). 

Similarities between [Ru(bpy),]2+ (discussed in Chapter 13) and [Pt,(pop)J4 are apparent. Reactive excited states are produced in each when it is subjected to visible light. The excited state ruthenium cation, [Ru(bpy)3]" +, can catalytically convert water to hydrogen and oxygen. The excited slate platinum anion, [Pt,(pop)J 4-, can catalytically convert secondary alcohols to hydrogen and ketones. An important difference, however, is that the ruthenium excited stale species results from (he transfer of an electron from the metal to a bpy ligand, while in the platinum excited state species the two unpaired electrons are metal centered. As a consequence, platinum reactions can occur by inner sphere mechanisms (an axial coordination site is available), a mode of reaction rot readily available to the 18-clectron ruthenium complex.-03... 

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