Catalytic reactions involving selectivity

Other catalytic reactions involving a transition-metal allenylidene complex, as catalyst precursor or intermediate, include (1) the dehydrogenative dimerization of tributyltin hydride [116], (2) the controlled atom-transfer radical polymerization of vinyl monomers [144], (3) the selective transetherification of linear and cyclic vinyl ethers under non acidic conditions [353], (4) the cycloisomerization of (V2V-dia-llyltosylamide into 3-methyl-4-methylene-(V-tosylpyrrolidine [354, 355], and (5) the reduction of protons from HBF4 into dihydrogen [238]. 

Thus, the Pd layer serves multiple purposes its surface catalyzes the dissociation of molecular hydrogen, it selectively forms palladium hydride, and it can be used as the metal gate of the field-effect devices. The scheme in Fig. 6.34 also shows the catalytic reaction involving oxygen. If both oxygen and hydrogen are present, the steady-state response of the Pd IGFET includes the surface-catalyzed oxidation. 

CO in exhaust gas (I). The objective of this study was to extend the approach to NO this entailed finding a suitable exothermic, selective, catalytic reaction involving NO in the presence of oxygen as well as the other constituents of exhaust gas. 

Catalytic reactions involving secondary alcohols on metal oxides are thought to proceed through mechanisms involving a cooperative action of acidic and basic sites. For the studied zeolites, a quasi-linear correlation was established between the alkene selectivities and the ratio of basic to acidic sites, as determined by adsorption calorimetry (Figure 13 see also Figure 6). 

Heterogeneous catalytic reactions involve by their nature a combination of reaction and transport processes, as the reactant must be first transferred from the bulk of the fluid phase to the catalyst surface. In Figure 11.2, the combined reaction and transport processes are shown schematically for a fast exothermic chemical reaction within a porous catalyst. If the rate of the intrinsic reaction is comparable to the rate of transport processes, significant concentration profiles of the reactants and products will develop. In addition, the temperature of the catalyst particle will be different from that of the bulk fluid. With increasing temperature, the influence of transport phenomena becomes more important and finally limits the overall reaction rate. This has detrimental influences on product yield and selectivity, and may lead to high overtemperatures of the catalyst and its fast deactivation [6]. The influence of transport phenomena is commonly characterized by an effectiveness factor as defined in Eq. (11.2). 

Further exploration of the higher activity of the Ni complexes compared to Pd analogs led to the discovery of a novel nano-sized catalytic system with superior performance for hydrothiolation and hydroselenation reactions of alkynes [ 152,153]. Furthermore, it was found that with a simple catalyst precursor - Ni(acac)2 - the reaction was carried out with excellent yields and excellent selectivity, even at room temperature. Both terminal and internal alkynes were successfully involved in the addition reaction. This catalytic system was tolerant to various functional groups in alkynes and was easily scaleable for the synthesis of 1-50 g of product (Scheme 3.85) [152, 153]. The proposed mechanism of the catalytic reaction involved (i) catalyst self organization with nano-sized particles formation, (ii) alkyne insertion into the Ni—Z bond and (iii) protonolysis with RZH (Scheme 3.86). 

Main-group examples of C-H activation, such as arene mercuration, are long known, but tend to involve stoichiometric reagents, not catalysts, and many use metals that are now avoided on toxicity grounds (Hg, Tl, and Pb). Catalytic reactions involving transition metal organometallic activation and functionalization of C-H bonds (Section 12.4) are beginning to move into the applications phase and are likely to become much more common in synthesis." " Innate selectivity can sometimes permit functionalization of one out of the many... 

The Jacobsen-Katsuki epoxidation reaction is an efficient and highly selective method for the preparation of a wide variety of structurally and electronically diverse chiral epoxides from olefins. The reaction involves the use of a catalytic amount of a chiral Mn(III)salen complex 1 (salen refers to ligands composed of the N,N -ethylenebis(salicylideneaminato) core), a stoichiometric amount of a terminal oxidant, and the substrate olefin 2 in the appropriate solvent (Scheme 1.4.1). The reaction protocol is straightforward and does not require any special handling techniques. 

The first application involving a catalytic reaction in an ionic liquid and a subsequent extraction step with SCCO2 was reported by Jessop et al. in 2001 [9]. These authors described two different asymmetric hydrogenation reactions using [Ru(OAc)2(tolBINAP)] as catalyst dissolved in the ionic liquid [BMIM][PFg]. In the asymmetric hydrogenation of tiglic acid (Scheme 5.4-1), the reaction was carried out in a [BMIM][PF6]/water biphasic mixture with excellent yield and selectivity. When the reaction was complete, the product was isolated by SCCO2 extraction without contamination either by catalyst or by ionic liquid. 

Few methodologies have either the diversity of synthetic transformations or the high level of product selectivity as catalytic reactions with the intermediate involvement of metal carbenes [ 1-5]. They provide synthetic opportunities that are clearly demonstrated in the preparation of the antidepressant sertraline (1)... 

Reactions involving the catalytic reduction of nitrogen oxides are of major environmental importance for the removal of toxic emissions from both stationary and automotive sources. As shown in this section electrochemical promotion can affect dramatically the performance of Rh, Pd and Pt catalysts (commonly used as exhaust catalysts) interfaced with YSZ, an O2 ion conductor. The main feature is strong electrophilic behaviour, i.e. enhanced rate and N2 selectivity behaviour with decreasing Uwr and , due to enhanced NO dissociation. 

As shown in Table 2.1, the improved catalytic performance of alkaline-treated zeolites compared to the parent purely microporous counterparts has been demonstrated decidedly by different groups active in academia and in industry. The positive effect is reflected in the enhanced activity, selectivity, and/or lifetime (coking resistance) of the hierarchical systems. The examples listed embrace not only a variety of zeohte topologies (MFl, MOR, MTW, BEA, and AST) but also reactions involving hghter hydrocarbons as well as bulky molecules. This illustrates the potential of the desihcation treatment, although more work is to be done in optimizing the catalytic system for the wide variety of applications. 

The Holy Grail of catalysis has been to identify what Taylor described as the active site that is, that ensemble of atoms which is responsible for the surface reactions involved in catalytic turnover. With the advent of atomically resolving techniques such as scanning tunnelling microscopy it is now possible to identify reaction centres on planar surfaces. This gives a greater insight also into reaction kinetics and mechanisms in catalysis. In this paper two examples of such work are described, namely CO oxidation on a Rh(llO) crystal and methanol selective oxidation to formaldehyde on Cu(llO). 

Enzymes are highly active catalysts in many biological processes. A very important feature in the catalytic action of enzymes is their high selectivity. Any enzyme that is active toward a particular reaction involving a particular substrate is entirely inactive toward other reactions and toward other substrates. (Note that in biochemistry, a substrate is the substance undergoing reaction under the catalytic effect of the enzyme.)... 

Intelligent engineering can drastically improve process selectivity (see Sharma, 1988, 1990) as illustrated in Chapter 4 of this book. A combination of reaction with an appropriate separation operation is the first option if the reaction is limited by chemical equilibrium. In such combinations one product is removed from the reaction zone continuously, allowing for a higher conversion of raw materials. Extractive reactions involve the addition of a second liquid phase, in which the product is better soluble than the reactants, to the reaction zone. Thus, the product is withdrawn from the reactive phase shifting the reaction mixture to product(s). The same principle can be realized if an additive is introduced into the reaction zone that causes precipitation of the desired product. A combination of reaction with distillation in a single column allows the removal of volatile products from the reaction zone that is then realized in the (fractional) distillation zone. Finally, reaction can be combined with filtration. A typical example of the latter system is the application of catalytic membranes. In all these cases, withdrawal of the product shifts the equilibrium mixture to the product. 

The methods available for synthesis have advanced dramatically in the past half-century. Improvements have been made in selectivity of conditions, versatility of transformations, stereochemical control, and the efficiency of synthetic processes. The range of available reagents has expanded. Many reactions involve compounds of boron, silicon, sulfur, selenium, phosphorus, and tin. Catalysis, particularly by transition metal complexes, has also become a key part of organic synthesis. The mechanisms of catalytic reactions are characterized by catalytic cycles and require an understanding not only of the ultimate bond-forming and bond-breaking steps, but also of the mechanism for regeneration of the active catalytic species and the effect of products, by-products, and other reaction components in the catalytic cycle. 

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