Cage catalysts

The same effect has been observed in the case of an encapsulated organogold catalyst of cycloi-somerization of enyne 441 by Scheme 5.23, and it has been attributed [22] to the hydrophobic environment within the coordination capsule 575, preventing carbenium-ionic intermediates of the catalytic process from their side reactions with water. The same caging catalyst has been used in [23] to perform the combined enzymatic and transition metal catalysis of tandem reactions by Scheme 5.24. The authors of this work also developed a tandem olefin isomerization-reduction reaction by Scheme 5.25 with the encapsulated organoruthenium cation as a catalyst on its... 

Chiral and Achiral Caging Catalysts and Cage Flasks... 

Activity of a (CH3)3PAu cation as a catalyst of intramolecular hydroalkoxylation of allenes became eight times higher upon its encapsulation within the cavity of the Ga4Lg coordination capsule 575. This allowed performing these reactions in water up to 67 catalytic turnovers by the caged catalyst have been observed in [34]. 

Much study has been devoted to the mechanisms of these reactions, but firm conclusions are still lacking, in part because the mechanisms vary depending on the metal, the R group, the catalyst, if any, and the reaction conditions. Two basic pathways can be envisioned a nucleophilic substitution process (which might be S l or Sn2) and a free-radical mechanism. This could be an SET pathway, or some other route that provides radicals. In either case, the two radicals R- and R would be in a solvent cage ... 

As surface area and pore structure are properties of key importance for any catalyst or support material, we will first describe how these properties can be measured. First, it is useful to draw a clear borderline between roughness and porosity. If most features on a surface are deeper than they are wide, then we call the surface porous (Fig. 5.16). Although it is convenient to think about pores in terms of hollow cylinders, one should realize that pores may have all kinds of shapes. The pore system of zeolites consists of microporous channels and cages, whereas the pores of a silica gel support are formed by the interstices between spheres. Alumina and carbon black, on the other hand, have platelet structures, resulting in slit-shaped pores. All support materials may contain micro, meso and macropores (see text box for definitions). 

Zeolites form a unique class of oxides, consisting of microporous, crystalline aluminosilicates that can either be found in nature or synthesized artificially [J.M. Thomas, R.G. Bell and C.R.A. Catlow in Handbook of Heterogeneous Catalysis (Ed. G. Ertl, H. Knbzinger and J. Weitkamp) (1997), Vol. 1, p. 206, VCH, Weinheim.]. The zeolite framework is very open and contains channels and cages where cations, water and adsorbed molecules may reside and react. The specific absorption properties of zeolites are used in detergents, toothpaste, and desiccants, whereas their acidity makes them attractive catalysts. 

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