Ruthenium, addition with

Alloys with ruthenium Additions of ruthenium have a most marked effect upon the hardness of platinum, but the limit of workability is reached at about 15% ruthenium, owing to the fact that ruthenium belongs to a crystallographic system different from that of platinum. Apart from a somewhat greater tendency to oxide formation at temperatures above 800°C, the resistance to corrosion of ruthenium-platinum alloys is comparable to that of iridium-platinum alloys of similar composition. 

As a final example in this section, a contribution by Grubbs et al. is discussed. The chloride-free ruthenium hydride complex [RuH2(H2)2(PCy3)2] (37) is believed to react, in the presence of alkenes, to form an unidentified ruthenium(O) species which undergoes oxidative additions with dihalo compounds, e.g., 38, to give the corresponding ruthenium carbene complex 9 (Eq. 4) [20]. 

Ultrathin-layer isoelectric focusing in polyacrylamide gels on polyester films was performed as described (Radola, 1980). Polygalacturonase activity was detected by the print technique with a dyed substrate (Ostazin Brilliant Red-D-galacturonan DP 10) (Markovic et al., 1992) or by the print technique with colouress D-galacturonan DP 10 dyed additionally with ruthenium red (Sigma, Germany). 

Fig. 3. Isoelectric focusing in ultrathin polyacrylamide layers (pH gradient 3 -10) of multiple forms of polygalacturonase produced by Candida boidinii under different cultivation conditions a - pectin, pH 3.51 b - pectin, pH 5.49 c -pectin, pH 7.01 d - 20% of D-galactopyranuronic acid in pectin e - pectate. A - Activity detection with print technique on colouress D-galacturonan DP 10 dyed additionally with ruthenium red ( both exo- and polygalacturonases) and B - activity detection with Ostazin Brilliant Red/D-galacturonan DP 10 agar print (polygalacturonases).

Similar additions of fj-keto esters to enones are catalyzed by ruthenium amides. With a chiral ligand, high levels of... 

In a formal sense, complexes 1 represent pre-catalysts that convert in the first turn of the catalytic cycle (vide infra) into ruthenium methylidene species of type 3 which are believed to be the actual propagating species in solution (Schemes 2,4). The ease of formation of 3 strongly depends on the electronic properties of the original carbene moiety in 1. In addition to complexes la-c with R1=CH=CPh2, ruthenium carbenes with Rx=aryl (e.g. Id, Scheme 3) constitute another class of excellent metathesis pre-catalysts, which afford the methylidene complex 3 after an even shorter induction period [5]. In contrast, any kind of electron-withdrawing (e.g. -COOR) or electron-donating substitu-... 

F-T Catalysts The patent literature is replete with recipes for the production of F-T catalysts, with most formulations being based on iron, cobalt, or ruthenium, typically with the addition of some pro-moter(s). Nickel is sometimes listed as a F-T catalyst, but nickel has too much hydrogenation activity and produces mainly methane. In practice, because of the cost of ruthenium, commercial plants use either cobalt-based or iron-based catalysts. Cobalt is usually deposited on a refractory oxide support, such as alumina, silica, titania, or zirconia. Iron is typically not supported and may be prepared by precipitation. 

Concerning the M=Co, bond, most of the reported examples result from inter- or intramolecular additions of anionic nucleophiles containing at least two reactive heteroatoms. Thus, sodium dimethyldithiocarbamate was found to react with the cationic allenylidene [RuTp(=C=C=CPh2)(PPh3)2] [PFg] (76) to generate the alle-nyl-metallacycle 77 (Scheme 26) as the result of the nucleophilic addition of one of the sulfur atoms at the Cq, carbon and subsequent coordination of the second sulfur to the ruthenium center, with concomitant release of a triphenylphosphine ligand [282]. Complex 77 could also be synthesized by treatment of the neutral derivative... 

Another focus of this chapter is the alkynol cycloisomerization mediated by Group 6 metal complexes. Experimental and theoretical studies showed that both exo- and endo- cycloisomerization are feasible. The cycloisomerization involves not only alkyne-to-vinylidene tautomerization but alo proton transfer steps. Therefore, the theoretical studies demonstrated that the solvent effect played a crucial role in determining the regioselectivity of cycloisomerization products. [2 + 2] cycloaddition of the metal vinylidene C=C bond in a ruthenium complex with the C=C bond of a vinyl group, together with the implication in metathesis reactions, was discussed. In addition, [2 + 2] cycloaddition of titanocene vinylidene with different unsaturated molecules was also briefly discussed. 

Bulk techniques still have a place in the search for presolar components. Although they cannot identify the presolar grain directly, they can measure anomalous isotopic compositions, which can then be used as a tracer for separation procedures to identify the carrier. There are several isotopically anomalous components whose carriers have not been identified. For example, an anomalous chromium component enriched in 54Cr appears in acid residues of the most primitive chondrites. The carrier is soluble in hydrochloric acid and goes with the colloidal fraction of the residue, which means it is likely to be submicron in size (Podosck el al., 1997). Measurements of molybdenum and ruthenium in bulk primitive meteorites and leachates from primitive chondrites show isotopic anomalies that can be attributed to the -process on the one hand and to the r- and /7-processes on the other. The s-process anomalies in molybdenum and ruthenium correlate with one another, while the r- and /7-process anomalies do not. The amounts of -process molybdenum and ruthenium are consistent with their being carried in presolar silicon carbide, but they are released from bulk samples with treatments that should not dissolve that mineral. Thus, additional carriers of s-, r-, and/ -process elements are suggested (Dauphas et al., 2002). 

Another regioselective addition to an epoxide was used as one step in a synthesis of the r-butyldiphenylsilyl ether (7) of verrucarinic acid from 5.3 The diol was converted into the optically active epoxy alcohol by the Sharpless method (10, 64-65) and then oxidized to the epoxy acid 6 by the new ruthenium-catalyzed oxidation of Sharpless et al. (this volume). This epoxy acid undergoes almost exclusive / -addition with trimethylaluminum to give the desired product 7. 

C-M bond addition, for C-C bond formation, 10, 403-491 iridium additions, 10, 456 nickel additions, 10, 463 niobium additions, 10, 427 osmium additions, 10, 445 palladium additions, 10, 468 rhodium additions, 10, 455 ruthenium additions, 10, 444 Sc and Y additions, 10, 405 tantalum additions, 10, 429 titanium additions, 10, 421 vanadium additions, 10, 426 zirconium additions, 10, 424 Carbon-oxygen bond formation via alkyne hydration, 10, 678 for aryl and alkenyl ethers, 10, 650 via cobalt-mediated propargylic etherification, 10, 665 Cu-mediated, with borons, 9, 219 cycloetherification, 10, 673 etherification, 10, 669, 10, 685 via hydro- and alkylative alkoxylation, 10, 683 via inter- andd intramolecular hydroalkoxylation, 10, 672 via metal vinylidenes, 10, 676 via SnI and S Z processes, 10, 684 via transition metal rc-arene complexes, 10, 685 via transition metal-mediated etherification, overview,... 

The ruthenium cluster Ru3(CO)12 and the RuCl2(CO)2(PPh3)2 system with ethyl or methyl iodide and additionally with diethyl amine as cocatalyst(s) have shown high catalytic activity in facile transformation of cyclic and acyclic amides to amines via hydrosilylation with many trisubstituted silanes (Eq. 94) [149],... 

In addition to these intramolecular [2+2+2] cycloadditions, intramolecular [4+2] cycloaddition of yne-enones 29 leading to fused pyrans 30 has been achieved by means of the ruthenium catalysis with a cationic complex, CpRu(MeCN)3PF6 (Eq. 15) [24], Such hetero Diels-Alder cycloaddition was considered to proceed via an oxaruthenacycle 31. 

Reduction with sodium naphthalene of easily obtained diazadiene ruthenium ) complexes of type 65 (X = Cl) affords (rj6-arene)Ru(0) complexes 64. The latter are very reactive and undergo oxidative addition with iodine or alkyl halides to produce complexes 65 (X = I and X = CH2R, respectively) (51) [Eq. (26)]. Other ruthenium(O) complexes have been... 

However, ruthenium, rhodium, and rhodium-platinum catalysts have been found to be highly effective for the selective hydrogenation of these benzyl-oxygen compounds without loss of the oxygen functions. Thus, benzyl alcohol is hydrogenated to cyclohexanemethanol in high yield over ruthenium dioxide with addition of a small amount of acetic acid (eq. 11.35).114... 

A better hydrogenation catalyst was generated by reaction of alkene metathesis ruthenium catalyst, with sodium hydride, after the RCM reaction was performed. In that case, hydrogenation can be performed under 1 bar of H2 at 20 °C [86]. Thus, cyclopentanols can be selectively prepared in one pot by RCM of the parents dienes, followed by addition of NaH and hydrogenation [86] (Scheme 40). 

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