Catalyst preparation systems

The same regioselective and stereospecific reactions are observed in decalin systems. The 3/3-formate 605 is converted into the a-oriented (j-allylpalladium complex 606, and the hydride transfer generates the fra .s-decalin 607, while the cis junction in 610 is generated from the 3tt-formate 608 by attack of the hydride from the /3-side (609). An active catalyst for the reaction is prepared by mixing Pd(OAc)2 and BU3P in a 1 I ratio with this catalyst the reaction proceeds at room temperature. The reaction proceeded in boiling dioxane when a catalyst prepared from Pd(OAc)2 and BujP in a 1 4 ratio was used[390]. 

Another group of isoprene polymerization catalysts is based on alanes and TiCl. In place of alkyl aluminum, derivatives of AlH (alanes) are used and react with TiCl to produce an active catalyst for the polymerization of isoprene. These systems are unique because no organometaHic compound is involved in producing the active species from TiCl. The substituted alanes are generally complexed with donor molecules of the Lewis base type, and they are Hquids or soHds that are soluble in aromatic solvents. The performance of catalysts prepared from AlHCl20(C2H )2 with TiCl has been reported (101). 

Fig. 2. LP Oxo gas recycle flow scheme A, feedstock pretreatment B, reactor C, catalyst preparation and treatment systems D, condenser E, separator F,...

Other workers have obtained higher yields of phenylethanol is absolute methanol the 90% yield reported above was probably due to traces of residual acid remaining from the catalyst preparation. Note that hydrogenolysis with this catalyst can be prevented completely by traces of base addition of base is often a useful means of preventing or minimizing unwanted hydrogenolysis in a variety of systems. 

A useful self-terminating catalyst system (77), employs a Pd catalyst [prepared from Pd(OAc)2, NaH, and r-AmOH in THF]. The solvent required for the hydrogenation depends on the acetylene structure monosubslituted acetylenes require solvents such as hexane or octane, whereas disubstituted acetylenes need ethanol, ethanol-hydrocarbon, or ethanol-THF mixtures. In all cases it was necessary to use quinoline as a catalyst modifier. The authors consider this system one of the best for achieving both high yield and stereoselectivity. 

The catalyst prepared above was characterized by X-ray diffraction, X-ray photoelectron and Mdssbauer spectroscopic studies. The catalytic activities were evaluated under atmospheric pressure using a conventional gas-flow system with a fixed-bed quartz reactor. The details of the reaction procedure were described elsewhere [13]. The reaction products were analyzed by an on-line gas chromatography. The mass balances for oxygen and carbon beb een the reactants and the products were checked and both were better than 95%. 

Kim and Somorjai have associated the different tacticity of the polymer with the variation of adsorption sites for the two systems as titrated by mesitylene TPD experiments. As discussed above, the TiCl >,/Au system shows just one mesitylene desorption peak which was associated with desorption from low coordinated sites, while the TiCl c/MgClx exhibits two peaks assigned to regular and low coordinated sites, respectively [23]. Based on this coincidence, Kim and Somorjai claim that isotactic polymer is produced at the low-coordinated site while atactic polymer is produced at the regular surface site. One has to bear in mind, however, that a variety of assumptions enter this interpretation, which may or may not be vahd. Nonetheless it is an interesting and important observation which should be confirmed by further experiments, e.g., structural investigations of the activated catalyst. From these experiments it is clear that the degree of tacticity depends on catalyst preparation and most probably on the surface structure of the catalyst however, the atomistic correlation between structure and tacticity remains to be clarified. 

A catalytic system Mo-V-Nb-W supported on alumina was prepared by impregnation and investigated for the selective oxidation of propane. The effects of the variation of each metal and of the catalyst preparation were analysed. The results show that Mo and V species supported on alumina can lead to catalysts with high selectivity to propene and reasonable selectivity to acrolein. The presence of Nb and W seems to have little effect. The catalyst can be affected by the method of impregnation. 

In the most effective, chirally modified catalytic systems, Pt/cinchonidine and Raney-Ni/tartaric acid, the enantioselectivity was also sensitive to the method of catalyst preparation and on support properties (5, 6). 

There is an absence of cis-to-trans isomerization with conversion or time for the C8 (1,5-cyclooctadiene) polymer. This is shown from 52 to 58% conversion after 1 to 16 hours reaction time in Table II and III. The above review (A0, A2, A3, A5) shows that the cis structure in polymers from 1,5-cyclooctadiene using various chloride catalysts fell below 50% cis even to 20% cis units this means that the second cis double bond from the monomer underwent extensive cis-to-trans isomerization following the ring-opening of the first cis bond. Where cis-2-butene isomerizes to trans structure using other catalyst preparations, there is no evidence of this for cis-2-butene using the iodine system. However, polymer molecular... 

Less clear is the sequence which leads to the formation of the active species in the case of catalysts prepared from zero-valent nickel complexes and aluminum halides or alkylaluminum halides (method C2). The catalytic properties of these systems, however—in particular, the influence of phosphines (76)—leaves no doubt that the active species is also of the HNiY type discussed above. In this connection, a recent electron spin resonance report that nickel(I) species are formed in the reaction of COD2Ni with AlBr3 (83 ), and the disproportionation of Ni(I) to Ni(II) and Ni(0) in the presence of Lewis acids (69) should be mentioned. 

The result of the calculations is that the calcined catalysts obtained from nitrate have dispersions between 5 and 15% only, whereas the Zr02 catalyst prepared from ethoxide has a favorable dispersion of 75 15% after calcination at 700 °C. The equivalent layer thickness for this system is 0.42 nm and the support coverage about 27%. Table 3.3 summarizes all results. 

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