Catalyst discussion

Butane-Based Fixed-Bed Process Technology. Maleic anhydride is produced by reaction of butane with oxygen using the vanadium phosphoms oxide heterogeneous catalyst discussed earlier. The butane oxidation reaction to produce maleic anhydride is very exothermic. The main reaction by-products are carbon monoxide and carbon dioxide. Stoichiometries and heats of reaction for the three principal reactions are as follows ... 

AT-heterocyclic carbenes show a pure donor nature. Comparing them to other monodentate ligands such as phosphines and amines on several metal-carbonyl complexes showed the significantly increased donor capacity relative to phosphines, even to trialkylphosphines, while the 7r-acceptor capability of the NHCs is in the order of those of nitriles and pyridine [29]. This was used to synthesize the metathesis catalysts discussed in the next section. Experimental evidence comes from the fact that it has been shown for several metals that an exchange of phosphines versus NHCs proceeds rapidly and without the need of an excess quantity of the NHC. X-ray structures of the NHC complexes show exceptionally long metal-carbon bonds indicating a different type of bond compared to the Schrock-type carbene double bond. As a result, the reactivity of these NHC complexes is also unique. They are relatively resistant towards an attack by nucleophiles and electrophiles at the divalent carbon atom. 

In contrast to the Pt catalysts discussed above, Ni based catalysts (i.e., also when supported on ZrO usually form coke at such a rapid rate that most fixed bed reactors are completely blocked after a few minutes time on stream (see Fig. 8) [16], The coke formed with the Ni catalysts is filamentous. The Ni particle remaining at the tip of the filament hardly deactivates as the coke formed on its surface seems to be transported through the metal particle into the carbon fibre, but the drastic increase in volume causes reactor plugging and prevents use of the still active catalyst (see Fig. 8). The TEM photographs indicate that the carbon filaments have similar diameters to those of the Ni particles. 

TS-1 is a material that perfectly fits the definition of single-site catalyst discussed in the previous Section. It is an active and selective catalyst in a number of low-temperature oxidation reactions with aqueous H2O2 as the oxidant. Such reactions include phenol hydroxylation [9,17], olefin epoxida-tion [9,10,14,17,40], alkane oxidation [11,17,20], oxidation of ammonia to hydroxylamine [14,17,18], cyclohexanone ammoximation [8,17,18,41], conversion of secondary amines to dialkylhydroxylamines [8,17], and conversion of secondary alcohols to ketones [9,17], (see Fig. 1). Few oxidation reactions with ozone and oxygen as oxidants have been investigated. 

TaniaPhos active catalyst discussion As shown by Salzer (2) such complexes with half sandwich stracture result in the catalyst cycle into a hydride species where the pentadienyl moiety can be hydrogenolyticaUy liberated (2, 6). This was verified in the case of BINAP complexes (2, diss. Podewils, Geyser). In accordance to this fact and other mechanistic aspects from Noyori s work (3, 5) it is likely that the pre-catalyst species undergoes the same reaction pathway and that the reactive part of the pre-catalyst, the pentadienyl moiety, will be liberated under hydrogenolytic conditions as shown below in Scheme 23.9 ... 

Entry 9 uses the oxaborazolidine catalysts discussed on p. 505 with 2-bromopropenal as the dienophile. The aldehyde adopts the exo position in each case, which is consistent with the proposed TS model. Entry 10 illustrates the use of a cationic oxaborazolidine catalyst. The chirality is derived from trans-1,2-diaminocyclohcxanc. Entry 12 shows the use of a TADDOL catalyst in the construction of the steroid skeleton. Entry 13 is an intramolecular D-A reaction catalyzed by a Cu-Ws-oxazoline. Entries 14 and 15 show the use of the oxazaborolidinone catalyst with more complex dienes. 

N anomaterials have been around for hundreds of years and are typically defined as particles of size ranging from 1 to 100 nm in at least one dimension. The inorganic nanomaterial catalysts discussed here are manganese oxides and titanium dioxide. Outside the scope of this chapter are polymers, pillared clays, coordination compounds, and inorganic-organic hybrid materials such as metal-organic frameworks. 

The homogeneous nickel catalysts discussed here2 have been prepared from a variety of nickel compounds the methods of preparation can be classified as follows ... 

Background information on the initial discovery and uses of the catalysts discussed in this section are to be found in Reference l. 

Though most of the catalysts discussed here are homogeneous, monoatomic species, it is possible to catalyze alkyne hydrosilylation by nanoparticles and polyatomic clusters.46 47 Recently, a report on this topic demonstrated the feasibility of using gold nanoclusters supported on alumina as a catalyst for alkyne hydrosilylation.48... 

Other salts of formic acid have been used with good results. For example, sodium and preferably potassium formate salts have been used in a water/organic biphasic system [36, 52], or with the water-soluble catalysts discussed above. The aqueous system makes the pH much easier to control minimal COz is generated during the reaction as it is trapped as bicarbonate, and often better reaction rates are observed. The use of hydrazinium monoformate salts as hydrogen donors with heterogeneous catalysts has also been reported [53]. 

As an illustration, consider the hydrogenation of propylene over a platinum alumina catalyst discussed in Section II. These date were taken from 0 to 35°C, 1 to 4 atm total pressure, and 0 to 45 % propylene. Equations (7) and (8) were obtained after considerable sifting and winnowing of rate equations. Both fit the observed data reasonably well. 

Tridentate ligands for cobalt and iron catalysts. The catalysts discussed earlier in the section on ethene oligomerisation can also be used for making polymers, provided that they are suitably substituted. In Figure 10.30 we have depicted such a catalyst, substituted with isopropyl groups at the aryl substituents on the imine group, as in Brookhart s catalysts [49], The initiation is now carried out by the addition of MAO to a salt of the cobalt or iron complexes. The catalysts obtained are extremely active, but they cannot be used for polar substrates. 

All the preliminary measurements of the Rh-3/5/Si02 (denoted as Rh-3-SILP) catalyst discussed so far were initially studied at 100 °C and 10 bar syngas pressure (H2 CO 1 1) over a period of up to 36 h. This time on stream was further extended to 180 hours to test the long-term stabihty of the Rh-3-SILP dehydroxylated catalyst system (Fig. 3). 

Reactions of allylic electrophiles with stabilized carbon nucleophiles were shown by Helmchen and coworkers to occur in the presence of iridium-phosphoramidite catalysts containing LI (Scheme 10) [66,69], but alkylations of linear allylic acetates with salts of dimethylmalonate occurred with variable yield, branched-to-linear selectivity, and enantioselectivity. Although selectivities were improved by the addition of lithium chloride, enantioselectivities still ranged from 82-94%, and branched selectivities from 55-91%. Reactions catalyzed by complexes of phosphoramidite ligands derived from primary amines resulted in the formation of alkylation products with higher branched-to-linear ratios but lower enantioselectivities. These selectivities were improved by the development of metalacyclic iridium catalysts discussed in the next section and salt-free reaction conditions described later in this chapter. 

This chapter is essentially a review of those ruthenium complexes which have been used as oxidation catalysts for organic substrates, emphasis being placed on such species which have been chemically well-defined and are effective catalysts. Of all the ruthenium oxidants dealt with here those which have the greatest diversity of use are RuO, [RuO ] , [RuO ], the tetramesityl porphyrinato (TMP) complex fran.y-Ru(0)2(TMP), RuCl3(PPh3)3, and cw-RuCl3(dmso). Many other catalysts are covered, and the uses of two principal starting materials, RuO. nH O and RuClj. nH O as precursors for a number of catalysts, discussed. 

Electrochemical reductions of CO2 at a number of metal electrodes have been reported [12, 65, 66]. CO has been identified as the principal product for Ag and Au electrodes in aqueous bicarbonate solutions at current densities of 5.5 mA cm [67]. Different mechanisms for the formation of CO on metal electrodes have been proposed. It has been demonstrated for Au electrodes that the rate of CO production is proportional to the partial pressure of CO2. This is similar to the results observed for the formation of CO2 adducts of homogeneous catalysts discussed earlier. There are also a number of spectroscopic studies of CO2 bound to metal surfaces [68-70], and the formation of strongly bound CO from CO2 on Pt electrodes [71]. These results are consistent with the mechanism proposed for the reduction of CO2 to CO by homogeneous complexes described earlier and shown in Sch. 2. Alternative mechanistic pathways for the formation of CO on metal electrodes have proposed the formation of M—COOH species by (1) insertion of CO2 into M—H bonds on the surface or (2) by outer-sphere electron transfer to CO2 followed by protonation to form a COOH radical and then adsorption of the neutral radical [12]. Certainly, protonation of adsorbed CO2 by a proton on the surface or in solution would be reasonable. However, insertion of CO2 into a surface hydride would seem unlikely based on precedents in homogeneous catalysis. CO2 insertion into transition metal hydrides complexes invariably leads to formation of formate complexes in which C—H bonds rather than O—H bonds have been formed, as discussed in the next section. 

Applications using hydrazine as a gas generator include tank pressurization, inflating pneumatic-power engine starters, turbines and positive displacement drives. The development of many of these uses was brought about by the introduction of decomposition catalysts discussed below in the section on combustion properties... 

Some of the supported (heterogenized) metal complex catalysts discussed above show good performance in the selective semihydrogenation of alkynes.446-449... 

The chiral Mo-based catalysts discussed herein are more sensitive to moisture and air than the related Ru-based catalysts [ 1 ]. However, these complexes, remain the most effective and general asymmetric metathesis catalysts and are significantly more robust than the original hexafluoro-Mo complex 1. It should... 

While use of the William s sludge catalyst, discussed above, and the exo-trans-exo isomer of 14 dramatically improves the isolable yield of diamantane (from 1 to 10 %), 20>31) the preparative utility of this reaction is limited. This problem is overcome using a different precursor. Hydrogenation of the Binor-S dimer of norbornadiene followed by rearrangement (Eq. (7)) gives diamantane in an average overall yield of 65 %3l ... 

The thiazolium and, particularly, triazolium catalysts discussed above have been developed to the extent that they perform remarkably well in the asymmetric benzoin condensation of aromatic aldehydes. Triazolium catalysts are also very effective in the (non-stereoselective) condensation of aliphatic aldehydes [250]. It seems, however, that no catalyst is yet available that enables condensation of aliphatic aldehydes with synthetically useful enantioselectivity. The best ee yet obtained are in the range 20-25%, e.g. in the dimerization of the straight-chain C2-C7 aldehydes [251]. 

The triazolium catalysts discussed above do not efficiently promote the Stetter reaction, i.e. the formation of 1,4-dicarbonyl compounds from aldehydes and a,/ -... 

The chiral Mo-based catalysts discussed herein are more senstive to moisture and air than the related Ru-based catalysts [1], However, these complexes, remain the most effective and general asymmetric metathesis catalysts and are significantly more robust than the original hexafluoro-Mo complex 1. It should be noted that chiral Mo-based catalysts 4,11, 25, 34 and 77 can be easily handled on a large scale. In the majority of cases, reactions proceed readily to completion in the presence of only 1 mol% catalyst and, in certain cases, optically pure materials can be accessed within minutes or hours in the absence of solvents little or no waste products need to be dealt with upon obtaining optically pure materials. Chiral catalyst 4a is commercially available from Strem, Inc. (both antipodes and racemic). The advent of the protocols for in situ preparation of chiral Mo catalyst 77, the supported and recyclable complex 82 and the debut of a chiral Ru catalyst (83) augur well for future development of practical chiral metathesis catalysts. The above attributes collectively render the chiral catalysts discussed above extremely attractive for future applications in efficient, catalytic, enan-tioselective and environmentally conscious protocols in organic synthesis. 

These catalytic reactions provide a unique pathway for addition of aromatic C-H bonds across C=C bonds. In contrast with Friedel-Crafts catalysts for olefin hydroarylation, the Ru-catalyzed hydrophenylation reactions of a-olefins selectively produce linear alkyl arenes rather than branched products. Although the selectivity is mild, the formation of anti-Markovnikov products is a unique feature of the Ru(II) and Ir(III) catalysts discussed herein. Typically, the preferred route for incorporation of long-chain linear alkyl groups into aromatic substrates is Friedel-Crafts acylation then Clemmensen reduction, and the catalysts described herein provide a more direct route to linear alkyl arenes. 

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