Dioxygen, catalytic

Competition between Homolytic and Heterolytic Catalytic Decompositions of Hydroperoxides Reactions of Transition Metals with Free Radicals Reactions of Transition Metal Ions with Dioxygen Catalytic Oxidation of Ketones Cobalt Bromide Catalysis Oscillating Oxidation Reactions... 

To avoid the dual problems of corrosion and high chloride concentrations, heteropolyoxo ions of the general formula [PMo,2 V O ] +" have been used in place of the CuVCu redox couple. The heteropolyoxo ions catalyze the reoxidation of Pd° to Pd + by dioxygen. Catalytic intermediates such as [PMo YjO ] and [PMo V O J are probably involved in this oxidation. Note that the oxidation state of one vanadium ion in the latter complex must be four. 

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... 

Volume 66 Dioxygen Activation and Homogeneous Catalytic Oxidation. Proceedings of the Fourth International Symposium on Dioxygen Activation and Homogeneous Catalytic Oxidation, Balatonfiired, September 10-14,1990 edited by L.l. Simandi... 

Scheme 10.27 Catalytic cycle of HppE. Dashed arrows indicate electron transport. In this scheme HPP binds to iron1". After a one-electron reduction, dioxygen binds and reoxidizes the iron center. The peroxide radical is capable of stereospecifically abstracting the (pro-R) hydrogen. Another one-electron reduction is required to reduce one peroxide oxygen to water. Epoxide formation is mediated by the resulting ironlv-oxo species.

Volume 66 Dioxygen Activation and Homogeneous Catalytic Oxidation. Proceedings of the... 

Simandi LI (2003) Advances in catalytic activation of dioxygen by metal complexes. Kluwer, Dordrecht... 

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-... 

Coutanceau C, El Hourch A, Crouigneau P, Leger JM, Lamy C. 1995. Conducting polymer electrodes modified by metal tetrasulfonated phthalocyanines Preparation and electro-catalytic behaviour towards dioxygen reduction in acid medium. Electrochim Acta 40 2739-2748. 

Anson FC, Ni CL, Saveant JM. 1985. Electrocatalysis at redox polymer electrodes with separation of the catalytic and charge propagation roles. Reduction of dioxygen to hydrogen peroxide as catalyzed by cobalt(II) tetrakis(4-A-methylpyridyl)porphyrin. J Am Chem Soc 107 3442. 

Durand RR Jr, Bencosme CS, Collman JP, Anson FC. 1983. Mechanistic aspects of the catalytic reduction of dioxygen by cofacial metalloporphyrins. J Am Chem Soc 105 2710. 

Bayer and Schretzmann 25) came to the conclusion that reversible oxygenation is a characteristic property of group VIII metals. However, work has shown that the cadmium complex CdEt2 can take up dioxygen reversibly in the ratio 1 2 (Cd O2). But it was found that the oxygenated complex (II(P) or 11(G) orientation) can undergo spontaneous catalytic oxidation to form bis(ethylperoxy) cadmium ... 

The direct use of dioxygen in the catalytic oxidation of nonactivated C-H bonds under mild conditions without using a coreductant was reported by using a K2Pt04/CuCl2 catalytic system to give the selective functionalization of a-amino acids in water.10 The aqueous medium avoided the need for protection of functional groups (Eq. 2.3). 

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). 

Electrocatalysis employing Co complexes as catalysts may have the complex in solution, adsorbed onto the electrode surface, or covalently bound to the electrode surface. This is exemplified with some selected examples. Cobalt(I) coordinatively unsaturated complexes of 2,2 -dipyridine promote the electrochemical oxidation of organic halides, the apparent rate constant showing a first order dependence on substrate concentration.1398,1399 Catalytic reduction of dioxygen has been observed on a glassy carbon electrode to which a cobalt(III) macrocycle tetraamine complex has been adsorbed.1400,1401... 

Dioxygen is a cheap and ideal source of oxygen but it is very difficult to activate and there are relatively few examples of 02 oxidations catalyzed by zeolite-encapsulated complexes. Encapsulated CoPc is active for the oxidation of propene to aldehyde, whereas the free complex is inactive.104 A triple catalytic system, Pd(OAc)2, benzoquinone, and a metal macrocycle, was used to oxidize alkenes with molecular oxygen at room temperature.105 Zeolite-encapsulated FePc106-108 and CoSalophen (Scheme 7.5)107109 complexes were used as oxygen-activating catalysts. With the use of a Ru complex instead of Pd(OAc)2 in the triple catalytic system, primary alcohols can be oxidized selectively to aldehydes.110... 

FIGURE 11.5 Chromatograms at 450nm of the reaction mixture at 6h of catalytic oxidation of 13-carotene by dioxygen catalyzed by ruthenium mesitylporphyrin. 

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