Bifunctional reaction pathway

The surface acid-base properties of bulk oxides can be conveniently investigated by studying the adsorption of suitably chosen basic-acidic probe molecules on the solid. Acidic and basic sites are often present simultaneously on solid surfaces. The two centers may work independently or in a concerted way, and the occurrence of bifunctional reaction pathways requiring a cooperative action of acidic and basic centers has also received considerable attention [39]. The acid-base properties of numerous amorphous metal oxides investigated by mrcrocalorime-try have been summarized in an extensive review by Cardona-Martinez and Dumesic [11]. 

The reaction pathway of 0-, N-, and S-containing l, 2-bifunctional benzenes with fluoroolefins depended on the relative abilities of the heteroatom to stabilize an adjacent anionic center, e.g., (17) and (18) [87-JCS(P1)763]. 

Dual-function catalysts possessing both metallic and acidic sites bring about more complex transformations. Carbocationic cyclization and isomerization as well as reactions characteristic of metals occurring in parallel or in subsequent steps offer new reaction pathways. Alternative reactions may result in the formation of the same products in various multistep pathways. Mechanical mixtures of acidic supports (silica-alumina) and platinum gave results similar to those of platinum supported on acidic alumina.214,215 This indicates that proximity of the active sites is not a requirement for bifunctional catalysis, that is, that the two different functions seem to operate independently. 

Hydrocarbon formation from methyl chloride can be catalyzed by ZSM-5482 483 or bifunctional acid-base catalysts such as W03 on alumina.420,447 The reaction on ZSM-5 gives a product distribution (43.1% aliphatics and 57.1% aromatics at 369°C) that is very similar to that in the transformation of methanol, suggesting a similar reaction pathway in both reactions.483 W03 on A1203 gives 42.8% C2-C5 hydrocarbons at 327°C at 36% conversion.447 When using methyl bromide as the feed, conversions are comparable. However, in this case, HBr can be very readily air-oxidized to Br2 allowing a catalytic cycle to be operated. Since bromine is the oxidant, the reaction is economical. The one step oxidative condensation of methane to higher hydrocarbons was also achieved in the presence of chlorine or bromine over superacidic catalysts.357... 

A problem with monofunctional reactions, e.g., cracking, alkylation, etc. is that they have a tendency to quickly deactivate because of coke deposition. This problem is usually not of concern with bifunctional reactions, e.g., those that employ a metal function in addition to the acid sites. However, we avoided the use of metal function because of the possible unknown modifications that could be introduced to a given sample by the metal deposition procedure. This is especially important when dealing with samples like VPI-5. Thus, to minimize the rate of deactivation, the alkylation experiments were conducted at 463 K. This low temperature introduces another problem, namely, the adsorption of reactants and products. At the experimental conditions employed here, the catalyst bed becomes saturated at time of 10 minutes or less (depending on sample). From this point onward, deactivation is clearly observable via the decrease in conversion with time. The data reported here were obtained at 11-13 minutes on-line. Since meta-diisopropylbenzene proceeds through several reaction pathways that lead to a number of products, it is most appropriate to compare the catalytic data at the constant level of conversion. Here we report selectivities at approximately 25 % conversion. For each catalyst, the results near 25 % conversion were repeated three times to ensure reproducibility. 

Mg-Al mixed oxides obtained by thermal decomposition of anionic clays of hydrotalcite structure, present acidic or basic surface properties depending on their chemical composition [1]. These materials contain the metal components in close interaction thereby promoting bifunctional reactions that are catalyzed by Bronsted base-Lewis acid pairs. Among others, hydrotalcite-derived mixed oxides promote aldol condensations [2], alkylations [3] and alcohol eliminations reactions [1]. In particular, we have reported that Mg-Al mixed oxides efficiently catalyze the gas-phase self-condensation of acetone to a,P-unsaturated ketones such as mesityl oxides and isophorone [4]. Unfortunately, in coupling reactions like aldol condensations, basic catalysts are often deactivated either by the presence of byproducts such as water in the gas phase or by coke build up through secondary side reactions. Deactivation has traditionally limited the potential of solid basic catalysts to replace environmentally problematic and corrosive liquid bases. However, few works in the literature deal with the deactivation of solid bases under reaction conditions. Studies relating the concerted and sequential pathways required in the deactivation mechanism with the acid-base properties of the catalyst surface are specially lacking. 

Scheme 30.3 The post-polymerization modification of hetero-bifunctional PS via consecutive thiol-ene and CuAAC coupling reactions. The identical click product is obtained from both reaction pathways. Adapted from Ref [49].

Scheme 1.46 A revised catalytic cycle for the asymmetric transfer hydrogenation of aromatic ketones in propan-2-ol by the Noyori-Ikariya (pre)catalyst 2 demonstrates crossover of the reaction pathways the product is obtained via a H"/H+ outer-sphere hydrogenation mechanism and/or step-wise metal-ligand bifunctional mechanism (see text). Formation of the major enantiomeric product is shown. (Adapted from Dub, P. A. et al., /. Am. Chem. Soc., 135, 2604-2619. Copyright 2013 American Chemical Society.)...

Ru adatoms not only promote methanol oxidation on ft at low potentials but also increase the current efficiency for CO2 generatiOTi. This can be explained by the facts that Ru adatoms can lower the oxidadmi potential of COads on ft, due to the bifunctional mechanism, and that low coverages of Ru adatoms can promote methanol dissociation to form COads on ft at low potentials, resulting from electronic effects. Therefore, Ru adatoms induce a shift from the reaction pathway via soluble intermediates to that via adsorbed CO. At potentials above +0.65 V, the current efficiency for CO2 generation during methanol oxidation on PtRu decreases, since Ru loses its co-catalytic activity at high potentials due to the formation of inactive Ru oxide. 

Abstract The concept of bifunctional acid catalysis is very helpful for inventing new catalytic asymmetric reactions. Compared with single functional acid catalysts, cooperative effect of two acid components has the potential to fine tune the reactivity as well as the selectivity of desired reaction pathways. This chapter focuses on some representative examples on the recent developments of bifunctional acid catalysis, including combined acid catalysis and other cooperative acid catalysis. 

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