Co-catalyzed systems

The effects of manganese on the cobalt/bromide-catalyzed autoxidation of alkylaromatics are summarized in Figure 17. The use of the Mn/Co/Br system allows for higher reaction temperatures and lower catalyst concentrations than the bromide-free processes. The only disavantage is the corrosive nature of the bromide-containing system which necessitates the use of titanium-lined reactors. 

The reaction rates of various types of olefins follow much the same pattern with both cobalt- and rhodium-catalyzed systems. Wender and co-workers (47) classified the nonfunctional substrates as straight-chain terminal, internal, branched terminal, branched internal, and cyclic olefins. The results they obtained are given in Table III. 

The C0/H20 systems have been used to catalyze hydrogenation of olefins in Reppe hydroformylation 437), and a Rh6(CO)16-catalyzed system has been used to reduce the olefinic bond in a,/3-unsaturated carbonyls and nitriles 337, 338, Section IV,A). 

Usually the stronger acids are also the more effective co-catalysts, but exceptions to this rule are known. Trichloroacetic acid, but not the equally strong picric acid, will co-catalyze the system isobutene-titanium tetrachloride in hexane.2 8 Some Lewis acid-olefin systems will not polymerize at all in the absence of a co-catalyst, an example being isobutene with boron trifluoride.2 4 This fact, together with the markedly slower reaction usual with carefully dried materials, has nourished the current suspicion that a co-catalyst may be necessary in every Lewis acid-olefin polymerization. It is very difficult to eliminate small traces of water which could act as a co-catalyst or generate mineral acid, and it may well be that the reactions which are slower when drier would not go at all if they could be made completely dry. 

Co2(CO)q system, reveals that the reactions proceed through mononuclear transition states and intermediates, many of which have established precedents. The major pathway requires neither radical intermediates nor free formaldehyde. The observed rate laws, product distributions, kinetic isotope effects, solvent effects, and thermochemical parameters are accounted for by the proposed mechanistic scheme. Significant support of the proposed scheme at every crucial step is provided by a new type of semi-empirical molecular-orbital calculation which is parameterized via known bond-dissociation energies. The results may serve as a starting point for more detailed calculations. Generalization to other transition-metal catalyzed systems is not yet possible. 

One involves hydroxide attack, leading to the formation of a metallocarboxylic acid (species 11 in Figure 6), and is evident in the Fe(CO) /base-catalyzed system ( 1). The other involves the formation of a readily hydrolyzable, zwitterionic metallocarboxa-mide, 12, in accord with the work of Edgell (35,36) and is evident in the Ru (CO) 2/NMe3 system. 

The precursor alloy is quenched to form small grains readily attacked by the caustic solution [31], Quenching can also enable specific intermetallic phases to be obtained, although this is less common. Yamauchi et al. [32-34] have employed a very fast quench to obtain a supersaturation of promoter species in the alloy. It is even possible to obtain an amorphous metal glass of an alloy, and Deng et al. [35] provide a review of this area, particularly with Ni, Ni-P, Ni-B, Ni-Co, and Ni-Co-B systems. The increased catalytic activity observed with these leached amorphous alloy systems can be attributed to either chemical promotion of the catalyzed reaction or an increased surface area of the leached catalyst, depending on the components present in the original alloy. Promotion with additives is considered in more detail later. 

The automatic procedure for reference spectra generation was first demonstrated for the start-up of a homogeneous catalyzed rhodium hydroformylation of cyclo-octene using Rh4(CO)i2 as precursor, n-hexane as solvent and FTIR as the in situ spectroscopy at 298 K [63]. The first n spectra were (i) empty spectrometer compartment (background), (ii) n-hexane at 0.2 MPa in a high pressure thermostatically controlled cell fitted with Cap2 windows (iii) system equilibrated with 2.0 MPa CO, (iv) system upon addition of cyclo-octene, and (v) system upon addition of Rh4(CO)i2. The n=l reference spectrum, which contained atmospheric... 

The high regio- and stereospecificity in the rhodium-catalyzed system does not seem to be compatible with the catalytic asymmetric synthesis using a chiral rhodium catalyst, and thus, there have so far been very few reports on the use of chiral rhodium catalysts for the asymmetric allylic alkylation. In 1999, Pregosin and his co-workers first reported asymmetric rhodium-catalyzed allylic alkylation of allylic esters (Equation (48)). Use of optically active... 

The carbonylative ring-expansion reaction via CO insertion into the N-O bond has been applied to the six-membered ring system, that is, oxazines, but using Co2(CO)g as the catalyst. For example, the Co-catalyzed reaction of oxazine 242 at 120 °C and 68 atm of CO gave oxazepinone 243 in 53% yield (Equation (19)). ... 

The activation parameters are presented in Table 819 For the reactions be between the Co(III) complex2+ and Fe-edta2-, (a) to (c) in Table 8, the activation enthalpy is smaller and the activation entropy larger than for the reduction by Fe2+, (d) to (f), which is a reaction of two cations. A comparison of the parameters for the polymer complex, (b) or (c), with those for the pyridine complex, (a) shows that the acceleration for the PVP or QPVP complex is based on a decrease in activation enthalpy and an increase in activation entropy. This is the opposite of the polyelectrolyte-catalyzed reaction, in which the acceleration is due to an increase in activation entropy (compare(e) with (d)). In the polyelectrolyte-catalyzed system the acceleration and increase in activation entropy are attributed to the increase in the local concentration of the two reactants, the Co(HI)-Py complex2 and Fe2+ 84, whereas in the reaction of the polymer complex the large activation entropy and small activation enthalpy are held to be due to the increase in the local concentration of the reactant Fe(II)-edta2 and the electrostatic attraction between the reactant and the Co(III) complex, which is fixed to the polycation chain. 

The dimeric [Ru(CO)o(OCOCH3) (pip)]2 complex (2) may be used at the appropriate ruthenium molarities to reproduce exactly the uptake plots observed with the polymeric catalyst. Solution IR measurements in regions of maximum activity for both 1- and 2-catalyzed systems showed the presence of the amine dimers which could be readily precipitated at any stage of the catalytic carbonylation by adding water. 

Reaction 4 shows that the ruthenium center with three coordinated carbonyls can transfer one such ligand to the piperidine (presumably coordinated). The mechanism suggested for the acetate complex includes exactly analogous steps (Reactions 6 and 7). The kinetics for the hydride-catalyzed system, however, are quite different and show a first-order dependence in Ru and a more complex dependence on CO (Figure 4). Further, no autocatalysis is evident. 

The rate law for the hydride-catalyzed system can be written as —d[CO]/dt = k [RuT] [pip], where k is a pseudo-second-order rate constant which includes the CO dependence. A mechanism which incorporates slow steps corresponding to Reactions 5 and 6 will lead to a rate law of the kind shown in Equation 11 which satisfies all the... 

Ishii and colleagues studied radical addition reactions of carbonyl compounds to olefins catalyzed by a Mn-Co catalytic system. Ketones 372a (R1=Alkyl) added... 

The indole oxidation has been shown to proceed via the hydroperoxide intermediate 9 (126), but whether this is formed via coordination catalysis, for example, as suggested in Reaction 41 for a phenol substrate (10— 12,13,14) (124), or via Haber-Weiss initiation, poses the same problem encountered in the organometallic type systems. A reactivity trend observed for Reaction 40 using tetraphenyl-porphyrin complexes (Co(II) Cu(II) Ni(II)) is reasonable in that the Co(II) system is known to give 1 1 02-adducts (at least, at low temperatures) but the reactivity trend also was observed for the catalyzed decomposition rate of 9. It is interesting to note that in Reac-... 

The TBAF-catalyzed allylation of aldehydes with 10 proceeds efficiently in refluxing THF.92 In contrast, a Pd-TBAF co-catalyst system enables the allylation at room temperature (Equation (20)).93 This mild allylation is due to the formation of a bis-7r-allylpalladium complex as the actual allylating agent. 

Mechanistically, alcohol carbonylation reactions catalyzed by the HCo(CO)4/ Co(CO)4 system appear to be governed by several features which are unique to this system. In particular, the high inherent acidity of the HCo(CO)4 species (45), coupled with the nucleophilicity of the conjugate base (55), is responsible for the activation of the substrate and formation of the alkyl-cobalt bond. In addition, the facility of homolytic cleavage of cobalt-carbon bonds (46, 47) may be responsible for the complications in selectivity not normally observed with other systems. 

Water-in-oil gel emulsions were tested in enzymatic aldolization of selected N-Cbz-amino aldehydes (Figure 19.3), N-Cbz-3-amino propanal (4), N-Cbz-glycinal, (5), (S)-N-Cbz-alaninal (6), and (R)-N-Cbz-alaninal (7) catalyzed by RAMA and L-rham-nulose-1-phosphate aldolase (RhuA) and L-fuculose-1-phosphate aldolase (FucA) from Escherichia coU [27,28]. The largest differences between conventional dimethyl formamide (DMF)/water co-solvent systems and gel emulsions were observed with RAMA and FucA catalysts (Figure 19.3). The emulsion media enhanced the catalytic efficiency of RAMA towards the N-Cbz amino aldehydes tested three, five. 

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