Carbon monoxide oxidation active centers

It is very likely that an excited halogen molecule suffers induced predissociation which is the first (initial) step of the given elementary reaction. Por this reason it may be considered that the halogen atoms are the primary active centers of halogen-sensitized photochemical reactions in virtually every case. A peculiar case of photosensitization with bromine has been observed for carbon monoxide oxidation [278]. The process Brg + hv ->2Br has been found to be followed by Br + O2 + CO -> BrO + CO2, etc. 

Carbon Monoxide (CO). At an activated gold electrode in alkaline (0.01 M NaOH) aqueous solution CO is oxidized to CO2- via a HO -centered ECE process (Figure 11.14) 20,21... 

The unique transformation of formamides to ureas was reported by Watanabe and coworkers [85]. In place of carbon monoxide, formamide derivatives are used as a carbonyl source. The reaction of formanilide with aniline was conducted in the presence of a catalytic amount of RuCl2(PPh3)3 in refluxing mesitylene, leading to N,AT-diphenylurea in 92% yield (Eq. 56) [85]. They proposed that the catalysis starts with the oxidative addition of the formyl C-H bond to the active ruthenium center. In the case of the reaction of formamide, HCONH2, with amines, two molecules of the amine react with the amide to afford the symmetrically substituted ureas in good yields. This reaction evolves one molecule of NH3 and one molecule of H2. 

After activation, the catalyst is intrcxiuced into the polymerization reactor as slurry in a saturated hydrocarbon such as isobutane. The precise mechanism of initiation is not known, but is believed to involve oxidation-reduction reactions between ethylene and chromium, resulting in formation of chromium (II) which is the precursor for the active center. Polymerization is initially slow, possibly because oxidation products coordinate with (and block) active centers. Consequently, standard Phillips catalysts typically exhibit an induction period. The typical kinetic profile for a Phillips catalyst is shown in curve C of Figure 3.1. If the catalyst is pre-reduced by carbon monoxide, the induction period is not observed. Unlike Ziegler-Natta and most single site catalysts, no cocatalyst is required for standard Phillips catalysts. Molecular weight distribution of the polymer is broad because of the variety of active centers. 

A high degree of hydrophobic character is an almost unique characteristic of silicon-rich or pure-silica-type microporous crystals. In contrast to the surface of crystalline or amorphous oxides decorated with coordinatively unsaturated atoms (in activated form), the silicon-rich zeolites offer a well-defined, coordinatively saturated sur ce. Such surfrces, based on the strong covalent character of the silicon-oxygen bond and the absence of hydrophilic centers, display a strong hydrophobic character unmatched by the coordinativeiy unsaturated, imperfect surfaces. Also, hydrophobic zeolite crystals have been reported to suppress the water affinity of transition metal cations contained in the zeolite pores. This property permits the adsorption of reactants such as carbon monoxide or hydrocarbons in the presence of water. 

The search for new reactivity and new reactions is an important target in homogeneous catalysis. A declared goal is the selective activation of C-H bonds under mild conditions. Although there are numerous examples of stoichiometric C-H bond oxidative additions to transition metal centers, successful examples regarding catalytic functionalization of C-H bonds have been made only during the last five years. Notable advances have been achieved by Moore and coworkers who described in 1992 the ortAo-acylation of pyridine with olefins and carbon monoxide. The cluster compound triruthenium dodecacarbonyl has been used as catalyst (Scheme 10). 

Studies (90, 91) with Cr02/Si02 catalyst have shown that formation of a surface chromate takes place by reaction of Cr02 and surface silanol groups on silica (Reaction 17). Reaction of this chemisorbed chromate with ethylene results in an oxidation-reduction reaction (90-95) with formation of a low-valent chromium center (Reaction 18). Proposals for Cr(II) as the active site are based on studies of the catalyst after reduction by ethylene, carbon monoxide, or hydrogen. One study (93. 94) showed that the polymerization rate increased with the fraction of Cr(II) in the catalyst. Another study (92) showed by polarography that the chromium is reduced to a divalent state by ethylene. 

The authors established directly the time scale for activation of C-H bonds in solutions at room temperature by monitoring the C-H bond activation reaction in the nanosecond regime with infrared detection. In the first stage of the process, loss of one carbon monoxide ligand (reaction VI-7 —- VI-8 in Scheme VI.6) substantially reduces back-bonding from the rhodium ion and increases the electron density at the metal center. Formed after the solvation stage, complex VI-9 traverses a 4.2 kcai nriol barrier (A = 5.0 x lo s ) and forms the -pCTp complex VI-10 which is more reactive toward C-H oxidative addition. 

Another Important concept introduced by Taylor was that of heterogeneity of surface-active centers.(25-26) This stemmed from observation of R. N. Pease that minute amounts of carbon monoxide, much smaller than the amount necessary to cover the surface, were sufficient to poison the surface of a copper catalyst. Taylor proposed that there were active centers on the surface while others argued that nickel impurities segregated preferentially on the surface and acted as catalyst. The variation of the heats of adsorption with surface coverage as determined by R. Beebe was used as evidence supporting the concept of active centers. In spite of the contradictory interpretation of the same experimental data, the concept of active centers has been a fruitful one. It inspired Imaginative research in the field of metal and oxide catalysis and has its present day expression in sophisticated surface physics studies. Subsequent work by coworkers of Turkevich at Princeton refined the nature of active centers in monodisperse metal particles and crystalline oxide catalysts. 

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