Ruthenium aqueous-phase conditions

The nitric acid solution from the dissolution of the fuel rod contents is filtered [poly(propene) fleece] or centrifuged, to remove suspended solids (zirconium- or molydenum- compounds and ruthenium and palladium alloys). The thus obtained fuel solution contains uranium, plutonium and the radioactive fission products. It is, after its composition is adjusted to the extraction conditions (3 molar in nitric acid and 240 to 300 g/L uranium) subjected to multi-cyclic extraction with tributylphosphate (dissolved in dodecane). Uranium and plutonium pass into the organic phase and are thereby separated from the fission products, which remain in the aqueous phase. 

The catalytic properties of the sulfonated diphosphine-stabilized RuNPs and sulfonated diphosphine/cyclodextrin-stabilized RuNPs were compared in the hydrogenation of unsaturated model substrates (styrene, acetophenone, and w-methylanisole) in biphasic liquid-hquid conditions (i.e., ruthenium aqueous colloidal solution and organic substrate no added solvent). Whilst all of these RuNPs displayed suitable performances in catalysis, different activities and selec-tivities were observed. This highhghted that supramolecular interactions on the metallic surface in the presence of a cyclodextrin control the catalytic reactivity of the nanocatalysts. Interestingly the CD acts as a phase-transfer promotor, which... 

Reduchon of carbonyls to give alcohol funchonalities is an important transformation in synthetic chemistry. Simple aldehydes and ketones can be hydrogenated under aqueous-phase catalysis. For instance, ruthenium in combination with TPPTS allows the hydrogenation of simple aliphatic aldehydes under either biphasic [52] or homogeneous [53] conditions. Thus, [Ru2(CO)4(OAc)(bipy)2][OAc] promoted the reduchon of acetone, affording 84% yield with a TOF of 133 h at 100 °C and 100 bar H2 in water in 24 h [54]. As shown in Scheme 6.5, subshtuted acetophenones were reduced with [Ir(cod) Cl]2 in the presence of a bipyridine ligand, showing >88% conversion in water at neutral pH [55]. 

In many respects the apparently analogous reduction of nitroarenes with triruthenium dodecacarbonyl under basic phase-transfer conditions is superior to that of the iron carbonyl-mediated reductions. However, the difference in the dependence of the two processes on the concentration of the aqueous sodium hydroxide and the pressure of the carbon monoxide suggests that they may proceed by different mechanisms. Although the iron-based system is most effective under dilute alkaline conditions in the absence of carbon monoxide, the use of 5M sodium hydroxide is critical for the ruthenium-based system, which also requires an atmosphere of carbon monoxide [11]. The ruthenium-based reduction has been extended to the... 

Ru/tppms catalysts exhibited excellent yields (98%) in the transfer hydrogenation of unsaturated aldehydes such as cinnamaldehyde or crotonaldehyde, to the corresponding unsaturated alcohols under mild reaction conditions (30-80°C), with HCOONa in an aqueous/organic two phase system. Similarly, ruthenium modified with the water soluble, air stable phosphine 100 (pta Table 5) is an effective catalyst for the chemoselective transfer hydrogenation of a,P-unsaturated aldehydes to unsaturated alcohols using formate in an aqueous/ organic two phase system. In contrast, Rh/pta afforded the cor-... 

---