Catalysts immobilized

Immobilized catalysts have also been described for the oxidation of water-insoluble olefins. Most work has been done with polymer-anchored palladium catalysts [18]. 

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Heterogeneous hydrogenation catalysts can be used in either a supported or an unsupported form. The most common supports are based on alurnina, carbon, and siUca. Supports are usually used with the more expensive metals and serve several purposes. Most importandy, they increase the efficiency of the catalyst based on the weight of metal used and they aid in the recovery of the catalyst, both of which help to keep costs low. When supported catalysts are employed, they can be used as a fixed bed or as a slurry (Uquid phase) or a fluidized bed (vapor phase). In a fixed-bed process, the amine or amine solution flows over the immobile catalyst. This eliminates the need for an elaborate catalyst recovery system and minimizes catalyst loss. When a slurry or fluidized bed is used, the catalyst must be separated from the amine by gravity (settling), filtration, or other means. 

As with organic solvents, proteins are not soluble in most of the ionic liquids when they are used as pure solvent. As a result, the enzyme is either applied in immobilized form, coupled to a support, or as a suspension in its native form. For production processes, the majority of enzymes are used as immobilized catalysts in order to facilitate handling and to improve their operational stability [24—26]. As support, either inorganic materials such as porous glass or different organic polymers are used [27]. These heterogeneous catalyst particles are subject to internal and external... 

Desai B, Kappe CO (2004) Microwave-Assisted Synthesis Involving Immobilized Catalysts. 

End N, Schoning K-U (2004) Immobilized Catalysts in Industrial Research and Application. 242 241-271... 

Clarke and Shannon also supported copper bis(oxazoline) complexes onto the surfaces of inorganic mesoporous materials, such as MCM-41 and MCM-48, through the covalent binding of the ligand, modified by alkoxysilane functionalities [59]. The immobilized catalysts allowed the cyclopropanation of styrene with ethyldiazoacetate to be performed as for the corresponding homogeneous case, and were reused once with almost no loss of activity or selectivity. 

Non-covalently Immobilized Catalysts Based on Chiral Salen Ligands. . 152... 

The mesoporous character of MCM-41 overcomes the size limitations imposed by the use of zeolites and it is possible to prepare the complex by refluxing the chiral ligand in the presence of Mn +-exchanged Al-MCM-41 [34-36]. However, this method only gives 10% of Mn in the form of the complex, as shown by elemental analysis, and good results are only possible due to the very low catalytic activity of the uncomplexed Mn sites. The immobihzed catalyst was used in the epoxidation of (Z)-stilbene with iodosylbenzene and this led to a mixture of cis (meso) and trans (chiral) epoxides. Enantioselectivity in the trans epoxides was up to 70%, which is close to the value obtained in solution (78% ee). However, this value was much lower when (E)-stilbene was used (25% ee). As occurred with other immobilized catalysts, reuse of the catalyst led to a significant loss in activity and, to a greater extent, in enantioselectivity. 

The enantioselectivity obtained in the hetero-Diels-Alder reaction (Scheme 12) was low (18% ee). This is, in part, due to the important temperature effect. For example, 50% ee was obtained in reactions carried out in homogeneous phase at - 60 °C and 95% ee in reactions at - 78 °C. However, at 0 °C the enantioselectivity dropped to 28% ee, a value closer to that obtained with the immobilized catalyst at the same temperature. Recycling was investigated and the solid was used four times with the same activity maintained. The 6b-Cu(OTf)2 catalyst proved to be less effective for this reaction and less stable in terms of recycling, a situation in agreement with the results obtained with exchanged catalysts [53]. 

Fig. 1. shows the P MAS NMR chemical shifts for the immobilized and homogeneous catalyst. The chemical shifts at the -15.2 and -13.7 ppm correspond to PTA while the chemical shifts in the range from 20 and 40 ppm correspond to phosphine oxide. The chemical shifts at the 66 and 118 ppm seems to be those of BINAP ligand, which is confirmed by the spectrum of Ru-BINAP catalyst. This spectrum shows that PTA exist in large amount on the surface of immobilized catalyst and that BINAP ligand is intact after immobilization. 

Fig. 1. P MAS NMR spectrum of (a)Ru-BrNAP/PTA/y-Al203, and (b)Ru-BINAP crt rlex In order to find the characteristics of the immobilized catalyst, asymmetric hydrogenation of the prochiral C=C bond was performed as a model reaction. Firstly, three different homogeneous Ru-BINAP complexes including [RuCl2((R)-BINAP)], [RuCl((R)-BINAP)(p-cymene)]Cl and [RuCl((R)-BINAP)(Benzene)]Cl were immobilized on the PTA-modified alumina. Reaction test of immobilized catalysts showed that [RuCl2((R)-BINAP)] was the most active and selective so all the experiment were done using this catalyst afterwards.

Reaction experiments were performed at the substrate to catalyst ratios between 250 and 5000 (Table 1). The immobilized catalyst showed a rather constant values of TOP and enantioselectivity in spite of the increase in the S/C ratio, even though these values were slightly lower than those of the homogeneous Ru-BINAP catalyst. After the reaction, the Ru content in the reaction mixture was measured by ICP-AES and was found to be under 2 ppm, the detecting limit of the instrument, indicating the at Ru metal didn t leach significantly during the reaction. These results show that the immobilized Ru-BINAP catalyst had stable activity and enantioselectivity and that the Ru metal complex formed a stable species on the alumina support. 

This result suggests that the reaction rate observed with the gel-immobilized catalysts is lower owing to the smaller concentration of the substrate inside the catalyst with respect to the liquid phase. This implies that the partition of substrates between the catalyst and the bulk liquid phase is fast. This could not be the case always and deviations... 

Another way of immobilizing catalyst complexes might be to trap them in the pores of solid particles, for instance by synthesizing the complex inside the pores of a zeolite ( ship in a bottle ). Another method could be to trap catalyst complexes in porous materials and deposit a membrane at the outer. surface. These methods of immobilizing a homogeneous catalyst do not involve chemical linkage between the catalyst and the carrier. The fixation is the result of steric hindrance. 

Laboratory reactor for studying three-phase processes can be divided in reactors with mobile and immobile catalyst particles. Bubble (suspension) column reactors, mechanically stirred tank reactors, ebullated-bed reactors and gas-lift reactors belong the class of reactors with mobile catalyst particles. Fixed-bed reactors with cocurrent (trickle-bed reactor and bubble columns, see Figs. 5.4-7 and 5.4-8 in Section 5.4.1) or countercurrent (packed column, see Fig. 5.4-8) flow of phases are reactors with immobile catalyst particles. A mobile catalyst is usually of the form of finely powdered particles, while coarser catalysts are studied when placing them in a fixed place (possibly moving as in mechanically agitated basket-type reactors). 

The patterned amine materials have been used to construct CGC-inspired sites that were evaluated in the catalytic polymerization of ethylene after activation with MAO. The complexes assembled on a porous silica surface using this methodology are more active than previously reported materials prepared on densely-loaded amine surfaces. This increased activity further suggests the isolated, unique nature of the metal centers. Work is continuing in our laboratory to further characterize the nature of the active sites, as well as to obtain more detailed kinetic data on the catalysts. The patterning methodology is also being applied to the creation of immobilized catalysts for small molecule reactions, such as Heck and Suzuki catalysis. 

The catalysts are referred to here as CGC-inspired because there is no evidence in the literature that illustrates that the immobilized catalysts have the same structure as homogeneous CGC catalysts. 

Immobilization of chiral complexes in PDMS membranes offers a method for the generation of new chiral catalytic membranes. The heterogenization of the Jacobsen catalyst is difficult because the catalyst loses its enantioselectivity during immobilization on silica or carbon surfaces whereas the encapsulation in zeolites needs large cages. However, the occlusion of this complex in a PDMS matrix was successful.212 The complex is held sterically within the PDMS chains. The Jacobsen catalyst occluded in the membrane has activity and selectivity for the epoxidation of alkenes similar to that of the homogeneous one, but the immobilized catalyst is recyclable and stable. 

Many challenges remain to be addressed in this field. The use of immobilized catalysts can often reduce the activity of a catalyst Reduced reaction rates due to diffusion limitations through a permeable membrane capsule and the ease or practicality of the synthesis of these catalyst scaffolds are issues that may pose problems. In some cases, these issues have been resolved, but this is often at the expense of other properties of the capsule. For example, the use of thin walls to reduce mass transfer limitations can be at the expense of nanocapsule strength and stability. 

Seebach and co-workers copolymerized a dendritically modified TADDOL ligand with styrene (Figure 9). When associated with Ti(OiPr)4, the immobilized catalyst gave a very high ee (98%) for more than 20 runs in the enantioselective addition of diethylzinc to benzaldehyde95 96... 

The other direction concerns the use of immobilized transition metal catalysts in the synthesis of libraries of organic compounds of interest in therapeutic drug discovery. One such strategy uses immobilized catalysts (e.g., scandium complexes), leading to efficient library syntheses of quinolines, amino ketones, and amino acid esters.72,73... 

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