Catalyst dioxygenating

These studies are part of a rare family of examples of the chemoselec-tive oxidation of catechols (150). The identification of the catalyst and the interception of the catalyst-dioxygen adduct are of particular relevance when the chemistry of catechol dioxygenase and tyrosinase enzymes is concerned. 

With higher alkenes, three kinds of products, namely alkenyl acetates, allylic acetates and dioxygenated products are obtained[142]. The reaction of propylene gives two propenyl acetates (119 and 120) and allyl acetate (121) by the nucleophilic substitution and allylic oxidation. The chemoselective formation of allyl acetate takes place by the gas-phase reaction with the supported Pd(II) and Cu(II) catalyst. Allyl acetate (121) is produced commercially by this method[143]. Methallyl acetate (122) and 2-methylene-1,3-diacetoxypropane (123) are obtained in good yields by the gas-phase oxidation of isobutylene with the supported Pd catalyst[144]. 

Ca.ta.lysis, Iridium compounds do not have industrial appHcations as catalysts. However, these compounds have been studied to model fundamental catalytic steps (174), such as substrate binding of unsaturated molecules and dioxygen oxidative addition of hydrogen, alkyl haHdes, and the carbon—hydrogen bond reductive elimination and important metal-centered transformations such as carbonylation, -elimination, CO reduction, and... 

Porphyrinic co-complexes as novel multinuclear catalysts for the reduction of dioxygen directly to water 97ACR437. 

Similarly, Dakka and coworkers oxidized a variety of substituted toluenes to the corresponding carboxylic acids using a Co /QBr catalyst in combination with dioxygen at 137-170 °C (Table 1). 

In one approach cyclohexane is autoxidized to a mixture of cyclohexanol and cyclohexanone in the presence of a Co or Mn naphthenate catalyst. This mixture is subsequently oxidized to adipic acid using nitric acid as the oxidant in the presence of a Cu Vv catalyst. An alternative method using dioxygen in combination with Co or Mn in HOAc gives lower selectivities to adipic acid (70% vs 95%). Alternatively, autoxidation in the presence of stoichiometric amounts of boric acid produces cyclohexanol as the major product, which is subsequently oxidized to adipic acid using HNO3 in the presence of Cu Vv. The latter step produces substantial amounts of N2O as a waste product. 

Mixed-valence Ru"-Ru" paddlewheel carboxylate complexes also have potential for oxidation reactions after incorporation in a microporous lattice with porphyrinic ligands. This MOF can be used for oxidation of alcohols and for hydrogenation of ethylene. Both the porosity of the lattice and the abihty of the diruthenium centers to chemisorb dioxygen are essential for the performance of the catalyst [62, 64]. 

Caris-Veyrat, C. et al., Cleavage products of lycopene produced by in vitro oxidations characterization and mechanisms of formation, J. Agric. Food Chem., 51, 7318, 2003. Caris-Veyrat, C. et al., Mild oxidative cleavage of beta, beta-carotene by dioxygen induced by a ruthenium porphyrin catalyst characterization of products and of some possible intermediates, New J. Chem., 25, 203, 2001. 

The oxidation of phenol, ortho/meta cresols and tyrosine with Oj over copper acetate-based catalysts at 298 K is shown in Table 3 [7]. In all the cases, the main product was the ortho hydroxylated diphenol product (and the corresponding orthoquinones). Again, the catalytic efficiency (turnover numbers) of the copper atoms are higher in the encapsulated state compared to that in the "neat" copper acetate. From a linear correlation observed [7] between the concentration of the copper acetate dimers in the molecular sieves (from ESR spectroscopic data) and the conversion of various phenols (Fig. 5), we had postulated [8] that dimeric copper atoms are the active sites in the activation of dioxygen in zeolite catalysts containing encapsulated copper acetate complexes. The high substratespecificity (for mono-... 

Partial oxidation reactions are usually carried out over transition metal oxides capable of changing their valent state during their interaction with reacting molecules. Naturally, zeolites with their alumina-silicate composition did not prove themselves as good oxidation catalysts. They failed also to serve as efScient catalyst supporters, since transition metals being introduced into the zeolite matrix lose their ability to activate dioxygen [3,4],... 

For this purpose we studied a temperature-programmed interaction of CH with a-oxygen. Experiments were carried out in a static setup with FeZSM-5 zeolite catalyst containing 0.80 wt % Fe203. The setup was equipped with an on-line mass-spectrometer and a microreactor which can be easily isolated from the rest part of the reaction volume. The sample pretreatment procedure was as follows. After heating in dioxygen at 823 K FeZSM-5 cooled down to 523 K. At this temperature, N2O decomposition was performed at 108 Pa to provide the a-oxygen deposition on the surface. After evacuation, the reactor was cooled down to the room temperature, and CH4 was fed into the reaction volume at 108 Pa. 

Feedstock Reactions Catalyst References Acetone Condensation-hydrogenation (bifunctional catalysis) Pd on sulfonated PS-DVB [6] Methanol, Raffinate II Condensation, hydrogenation Pd on sulfonated PS-DVB [61] Dioxygen dissolved in water Hydrogenation Pd on sulfonated PS-DVB [8]... 

Paradoxically, all these significant recent contributions to the theory of the ORR, together with most recent experimental efforts to characterize the ORR at a fuel cell cathode catalyst, have not led at aU to a consensus on either the mechanism of the ORR at Pt catalysts in acid electrolytes or even on how to properly determine this mechanism with available experimental tools. To elucidate the present mismatch of central pieces in the ORR puzzle, one can start from the identification of the slow step in the ORR sequence. With the 02-to-HOOads-to-HOads route appearing from recent DFT calculations to be the likely mechanism for the ORR at a Pt metal catalyst surface in acid electrolyte, the first electron and proton transfer to dioxygen, according to the reaction... 

For the ascending branch of the volcano plot, the term (1/Z + 1) could serve by itself as an effective ORR activity predictor, whereas, for the descending branch, (1/Z + 1) becomes close to unity at 0.85 V, and the exponential factor exp(—A//, /R70, then determines the ORR rate based on the residual interaction of dioxygen with the (excessively) noble metal catalyst surface. 

Demarconnay L, Coutanceau C, Leger JM. 2004. Electroreduction of dioxygen (ORR) in alkaline medium on Ag/C and F t/C nanostractured catalysts-effect of the presence of methanol. Electrochim Acta 49 4513-4521. 

Pahnore GTR, Bertschy H, Bergens SH, Whitesides GM. 1998. A methanol/dioxygen biofuel cell that uses NAD -dependent dehydrogenases as catalysts Application of an electro-enzymatic method to regenerate nicotinamide adenine dinucleotide at low overpotentials. J Electroanal Chem 443 155-161. 

Guilard R, Brandes S, Tardieux C, Tabard A, L Her M, Miry C, Gouerec P, Knop Y, Collman JP. 1995. Synthesis and characterization of cofacial metaUodiporphyrins involving cobalt and lewis acid metals New dinuclear multielectron redox catalysts of dioxygen reduction. J Am Chem Soc 117 11721. 

YuasaM, Nishfliara R, Shi C, Anson EC. 2001. A comparison of several meso-tetraalkyl cobalt porphyrins as catalysts for the electroreduction of dioxygen. Pol) Adv Technol 12 266. 

It is rather difficult to study function 2 separately, as the catalyst generally presents, simultaneously, functions 1 and/or function 3. Nevertheless, the mild interaction of HC with N02 can be approached through the direct N02/HC reaction, even in the absence of dioxygen. It has to be compared to the total oxidation of HC in the presence of oxygen, as it is a competitive reaction for the HC consumption. In contrast, it will be very interesting to compare the two catalytic pathways of elementary steps, and reaction intermediates, in both oxidation reactions (mild and total oxidation of reductant). 

---