Silica-supported Systems

Early work in this area has involved the investigation of the olefin metathesis activity of [W( Bu)(CH 2Bu)J supported on silica or other oxide supports [65, 66]. While highly active, these systems do not contain a metallocarbene [40, 67]. For instance, the silica-supported system has been characterized as [ iOW( Bu)(CH 2Bu)J, and therefore it is very likely that the propagating metallocarbene is generated in situ even if it is not clear how it is formed. [ iOMo( Bu)(CH 2Bu)J also displays similar reactivity towards olefins, but is more sensitive to functional groups [67, 68]. For tantalum, despite the presence of a weU-defined metallocarbene in [( iO)Ta(=CH Bu)(CH 2Bu)J, this system is... 

Other Friedel-Crafts catalysts are also being developed these include clay-supported metal halides [32] and mesoporous silica supported systems [33], Even enzymes can be used to perform Friedel-Crafts reactions [34]. 

The metal content was varied in two experimental series, with the results listed in Table 16.4. Both y-alumina and silica exhibit a maximum STY for a catalyst loading of 2g etaigrupporf In the case of y-alumina, an STY of 65.1 kgco, ms,Lp- h- is reached at this loading, which is about 15 times the value of the silica-supported system. For both support materials, the TOF decreases for increasing amounts of the active component. This may be related to a beginning mass-transfer hmitation... 

Just as for polymer-supported catalysts [9], small proUne-containing peptides have been supported on mesoporous materials as well [54]. As for systems founded on organic polymers, silica-supported systems can also give high catalytic selectivity and activity, and can also be successfully recycled. 

The type of CSPs used have to fulfil the same requirements (resistance, loadabil-ity) as do classical chiral HPLC separations at preparative level [99], although different particle size silica supports are sometimes needed [10]. Again, to date the polysaccharide-derived CSPs have been the most studied in SMB systems, and a large number of racemic compounds have been successfully resolved in this way [95-98, 100-108]. Nevertheless, some applications can also be found with CSPs derived from polyacrylamides [11], Pirkle-type chiral selectors [10] and cyclodextrin derivatives [109]. A system to evaporate the collected fractions and to recover and recycle solvent is sometimes coupled to the SMB. In this context the application of the technique to gas can be advantageous in some cases because this part of the process can be omitted [109]. 

A significant volume of literature relates to our work. Concerning choice of support, Montassier et al. have examined silica-supported catalysts with Pt, Co, Rh Ru and Ir catalysts.However, these systems are not stable to hydrothermal conditions. Carbon offers a stable support option. However, the prior art with respect to carbon-supported catalysts has generally focused on Ru and Pt as metals.Additionally, unsupported catalysts have also been reported effective including Raney metals (metal sponges).Although the bulk of the literature is based on mono-metallic systems, Maris et al. recently reported on bimetallic carbon-supported catalysts with Pt/Ru and Au/Ru. In contrast, our work focuses primarily on the development of a class of rhenium-based carbon supported catalysts that have demonstrated performance equal to or better than much of the prior art. A proposed reaction mechartism is shown in Figure 34.2 °l... 

Silica-supported heterogenous Cr systems, such as the Phillips247,248 and Union Carbide catalysts,249,250 are used in the commercial production of polyethylene. The active sites are widely agreed to contain low-valent Cr centers. The relatively ill-defined nature of these catalysts has led to considerable efforts to synthesize well-defined homogeneous Cr-based catalysts. 

Silica gel-based catalytic systems have been described as efficient promoters for a number of organic reactions.28 Illustrative examples include the oxidative cleavage of double bonds catalyzed by silica-supported KM11O4,29 reaction of epoxides with lithium halides to give /i-halohydrins performed on silica gel,30 selective deprotection of terf-butyldimethylsilyl ethers catalyzed by silica gel-supported phosphomolybdic acid (PMA),31 and synthesis of cyclic carbonates from epoxides and carbon dioxide over silica-supported quaternary ammonium salts.32... 

Silica-supported reagents have been exploited as nontoxic, inexpensive, reusable, and environmentally acceptable catalysts for developing stoichiometric reaction methods in organic chemistry and specifically in carbohydrate chemistry. Apart from being easy to handle and to store, these systems allow facile workup, the catalyst being removed by simple filtration, and the reaction products isolated by chromatographic purification, if necessary. 

Mortreux and co-workers compared the activity of the SAPC catalysts with that of the homogeneous analogue in the hydroformylation of methyl acrylate [69]. They observed an activity for the SAPC that was strongly dependent on the amount of water present in the system. More remarkably, the optimised activity of the SAPC was higher than that of the homogeneous systems. This effect was ascribed to the polar interactions between the substrate and the silica support. This effect was not observed for nonpolar substrates such as propene, which supported the hypothesis. 

For several silica-supported catalysts in condensed phase, including the SAPC system, the rates are disappointing. This can be assigned to slow mass transfer, and perhaps to incomplete rhodium hydride formation as we have discussed and observed. The sol-gel catalyst is relatively fast and is sometimes only a few times slower than the homogeneous one. Since only limited ways of preparation were tested, there is probably more scope for sol-gel catalysts. Space-time yields are promising at the present state of affairs. 

In addition to other polystyrene [138] and silica supports [139, 140, 141, 142, 143,144], iron and cobalt precatalysts have been immobilised on calcosilicate [145], magnesium dichloride [146,147,148,149], MCM-41 zeolite [150,151], clay [152] and fluorotetrasilicic mica [153], Supported systems have also been examined using alternative activators [154, 155, 156, 157, 158, 159]. For example, silica- and alumina-supported samples 5 have been activated with AK/ -Bu), to afford highly active, thermally robust catalysts [154], IR spectroscopy in DRIFT mode... 

As already mentioned, the acidity of the HY zeolite precludes its use as a support for Fe3(C0)- 29 then iron particles. The same behaviour is observed for Fe3(C0) 2 silica alumina system. This material, when decomposed at 200°C is not an efficient catalyst for F-T synthesis and only C-j-C products are... 

The hydrogenation catalysts can be prepared in situ, starting from the surface alkyl complex. In terms of catalytic performances, these catalysts are highly effective (Table 6.21) [150]. The best hydrogenation systems are based on silica supported dinuclear complexes, for which the structures of the active sites have not been investigated. Hydrogenation of toluene and xylenes can be achieved under similar conditions. 

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