Solvent effects cluster synthesis

A particularly broad potential for application in syngas reactions is shown by ruthenium carbonyl clusters. Iodide promoters seem to favor ethylene glycol (155,156) the formation of [HRu3(CO),]- and [Ru(CO)3I3]- was observed under the catalytic conditions. These species possibly have a synergistic effect on the catalytic process. Imidazole promoters have been found to increase the catalytic activity for both methanol and ethylene glycol formation (158-160). Quaternary phosphonium salt melts have been used as solvents in these cases the anion [HRu3(CO)u] was detected in the mixture (169). Cobalt iodide as cocatalyst in molten [PBu4]Br directs the catalytic synthesis toward acetic add (163). With... 

The oxidizing superacids are versatile and effective for the generation of clusters in solution but severe difficulties are associated with crystallization and recovery of solid cluster phases. These difficulties were to a great extent overcome by the observation that the pentaffuorides of antimony and, even better, arsenic in super-acidic or inert solvents quantitatively oxidize post-transition elements to cationic clusters. The method was presented in 1969 and was first used in the synthesis of the (AsFfi)" salt of (Ss)" 4 in HF solution, according to reaction (7). ° ... 

Such a reaction of Fe(CO)5 (at 293-363 K, PVP) without ultrasonic radiation proceeds very slowly and only after few days there, a material is formed with very low Fe content (2%, the isolated particles 2-5 nm in size). It is of interest that the sonochemical decomposition of Fe(CO)5 does not proceed in the presence of PVP if THF is used as the solvent, but the reaction is very effective when anisole is used as the solvent and PFO is used as the polymer matrix [93]. A black product formed contains up to 10% (in mass) of the spheric particles of nonoxidized Fe (mainly y-Fe, with little content of a-Fe) with 1-12 nm in size (the mean diameter is 3nm, as shown in Figure 3.7). It is likely that the big particles present the flocks of little ones ( 2-2.5nm). The sonochemical synthesis allows us to produce the functionalized amorphous nanoparticles of ferric oxide with 5-16 nm in diameter [94]. The ultrasonic irradiation in the PFO presence allows us to also produce the stabilized nanoparticles of copper, gold, and so on. In the literature the findings are not about the bimetallic particle formation in the ultrasonic fields by carbonyl metal reduction in the polymer matrices presence (as, for example, in the case of the carbon-supported Pt-Ru from PtRu5C(CO)i6 reduced clusters [95]). 

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