Hydrogenation reactions, 804 table

Hydrogenation Reactions (Table 2) 1.2 equivalents of supported ligand were gently stirred in a schlenk flask with 1 equivalent [Rh(COD)2lBF4 dissolved in 3 ml methanol, until the support was orange and the solution colourless. This process was fast for all ligands (< 5min.) except for Im (about 1... 

The complex Na[Ru3(/r-H)(CO)n] (9) is the only anionic ruthenium cluster reported to promote an alkyne hydrogenation reaction (Table 1, entry 10). It has been found to reduce diphenylacetylene selectively to Z-stilbene, in dimethylformamide under moderate pressure, but no further details have been given. ... 

Scheme 1.1 First examples of enantioselective hydrogenation reactions (Table 1.1).

Heat of combustion, 113 Heat of hydrogenation, 186 table of, 187 Heat of reaction, 154 Helicase, DNA replication and, 1106 Hell-Volhard-Zelinskii reaction, 849 amino acid synthesis and. 1025 mechanism of, 849 Heme, biosynthesis of, 966 structure of, 946 Hemiacetal, 717 Hemiketal, 717 Hemithioacetal, 1148 Henderson-Hasselbalch equation,... 

Alkali metal A metal in Group 1 of the periodic table, 31 hydrogen reactions with, 542 oxygen reactions with, 543-544 reactions of, 541t, 552q water reactions with, 542... 

If, for the purpose of comparison of substrate reactivities, we use the method of competitive reactions we are faced with the problem of whether the reactivities in a certain series of reactants (i.e. selectivities) should be characterized by the ratio of their rates measured separately [relations (12) and (13)], or whether they should be expressed by the rates measured during simultaneous transformation of two compounds which thus compete in adsorption for the free surface of the catalyst [relations (14) and (15)]. How these two definitions of reactivity may differ from one another will be shown later by the example of competitive hydrogenation of alkylphenols (Section IV.E, p. 42). This may also be demonstrated by the classical example of hydrogenation of aromatic hydrocarbons on Raney nickel (48). In this case, the constants obtained by separate measurements of reaction rates for individual compounds lead to the reactivity order which is different from the order found on the basis of factor S, determined by the method of competitive reactions (Table II). Other examples of the change of reactivity, which may even result in the selective reaction of a strongly adsorbed reactant in competitive reactions (49, 50) have already been discussed (see p. 12). 

The hydrogen abstraction addition ratio is generally greater in reactions of heteroatom-centered radicals than it is with carbon-centered radicals. One factor is the relative strengths of the bonds being formed and broken in the two reactions (Table 1.6). The difference in exothermicity (A) between abstraction and addition reactions is much greater for heteroatom-centered radicals than it is for carbon-centered radicals. For example, for an alkoxy as opposed to an alkyl radical, abstraction is favored over addition by ca 30 kJ mol"1. The extent to which this is reflected in the rates of addition and abstraction will, however, depend on the particular substrate and the other influences discussed above. 

Table 1 Olefin hydrogenation reactions catalyzed by iron complexes...

Substances which react with water to liberate flammable gas, e.g. carbides (liberate acetylene), alkali metals (hydrogen), organometallics (hydrocarbons - see Table 6.8), and where the heat of reaction is sufficient to ignite the gas. Thus metals which are less electronegative than hydrogen (see Table 6.10) will displace this element from water or alcohols, albeit at different rates. 

The kinetics of ethylene hydrogenation on small Pt crystallites has been studied by a number of researchers. The reaction rate is invariant with the size of the metal nanoparticle, and a structure-sensitive reaction according to the classification proposed by Boudart [39]. Hydrogenation of ethylene is directly proportional to the exposed surface area and is utilized as an additional characterization of Cl and NE catalysts. Ethylene hydrogenation reaction rates and kinetic parameters for the Cl catalyst series are summarized in Table 3. The turnover rate is 0.7 s for all particle sizes these rates are lower in some cases than those measured on other types of supported Pt catalysts [40]. The lower activity per surface... 

Table 3. Ethylene hydrogenation reaction rates and kinetic parameters for both series of Pt/SBA-15 catalysts [13,16].

Table 3 Results obtained for hydrogen transfer and hydrogenation reactions in different conditions using Cu/Si02 as catalyst.

Metal NPs immobilized in ILs are highly active and recyclable for hydrogenation reactions in multiphase systems (see Scheme 1.2, Table 1.2, and Figure 1.5). 

Oheme and co-workers investigated335 in an aqueous micellar system the asymmetric hydrogenation of a-amino acid precursors using optically active rhodium-phosphine complexes. Surfactants of different types significantly enhance both activity and enantioselectivity provided that the concentration of the surfactants is above the critical micelle concentration. The application of amphiphilized polymers and polymerized micelles as surfactants facilitates the phase separation after the reaction. Table 2 shows selected hydrogenation results with and without amphiphiles and with amphiphilized polymers for the reaction in Scheme 61.335... 

HTAB has been used, on the one hand, to increase the CL intensity of the reaction of 2,6,7-trihydroxy-9-(4 chlorophenyl)-3-fluorene with hydrogen peroxide in alkaline solution, in the presence of traces of Co(II) as a catalyst [43]. As a consequence, a CL method has been established for determination of ultratraces of Co(II). On the other hand, HTAB micelles sensitize the CL oxidation of pyro-gallol with A-bromosuccimide in an alkaline medium [44], while anionic and nonionic surfactants inhibit the CL intensity of this reaction (Table 3). This sensitized process allows the determination of pyrogallol by flow injection in an interval of 5 X 10 7-3 X 10 5 M. 

Hydrogenation reactions with LiAlH4 and addition of acidic compounds XH, afford good derivatizing and scavenging schemes for compounds like 66 (see Table 6), which are very reactive149. For example, compounds 29, 30 (Table 4), 40 and 41 (Table 5) are derived in such a manner. 

Linn and Halpern later found that the active catalyst in the ketone and anthracene hydrogenation reactions of Pez was likely to be Ru( 2-H2)(H)2(PPh3)3 (Fig. 3.6) [67]. For example, cyclohexanone is converted to cyclohexanol under mild conditions in toluene (see Table 3.3). The TOF depends on the substrate concentration, and the rate law for the catalytic reaction was determined to be given by Eq. (2), with k= 1.3x 10 M-1 s-1 at 20°C. 

Table 9.11 Hydrogenation reactions with Pd nanocatalysts in methanol, toluene or [BMIM][PF6].a) (Adapted from [77])...

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