Oxygen activation: theory

A number of transition metals are now known147-156 to form stable dioxygen complexes, and many of these reactions are reversible. In the case of cobalt, numerous complexes have been shown to combine oxygen reversibly.157 158 Since cobalt compounds are also the most common catalysts for autoxidations, cobalt-oxygen complexes have often been implicated in chain initiation of liquid phase autoxidations. However, there is no unequivocal evidence for chain initiation of autoxidations via an oxygen activation mechanism. Theories are based on kinetic evidence alone, and many authors have failed to appreciate that conventional procedures for purifying substrate do not remove the last traces of alkyl hydroperoxides from many hydrocarbons. It is usually these trace amounts of alkyl hydroperoxide that are responsible for chain initiation during catalytic reaction with metal complexes. 

D. Rutkowska-Zbik, R. Tokarz-Sobieraj, M. Witko, Quantum chemical description of oxygen activation process on Co, Mn, and Mo porphyrins, ]. Chem. Theory Comput. 3 (2007) 914. 

Key words molecular mechanics, DFT, ligand-field theory, oxygen activation, Jahn-Teller distortion, distortional isomer... 

The existence of those mixed function oxidases illustrates the complexity of the problem of oxygen activation. In order to transform the complex problem into a number of more simple ones, model experiments have been devised. They may or may not contribute to the elucidation of the enzymic mechanism. Making our way through the wealth of theories based on enzyme and model experiments, we shall follow a double track one path leads to an understanding of the chemical properties of the oxygen molecule the other path, to deeper insight into the catalytic processes in which it is engaged. 

Langmuir s research on how oxygen gas deteriorated the tungsten filaments of light bulbs led to a theory of adsorption that relates the surface concentration of a gas to its pressure above the surface (1915). This, together with Taylor s concept of active sites on the surface of a catalyst, enabled Hinshelwood in around 1927 to formulate the Langmuir-Hinshelwood kinetics that we still use today to describe catalytic reactions. Indeed, research in catalysis was synonymous with kinetic analysis... 

Anderson AB, Roques J, Mukeijee S, Murthi VS, Markovic NM, Stamenkovic V. 2005. Activation energies for oxygen reduction on platinum alloys Theory and experiment. J Phys Chem B 109 1198-1203. 

An electrochemical theory has been applied to explain the mechanisms of adsorption of metal ions on activated charcoal (carbon). According to this theory, oxygen in contact with an aqueous suspension of charcoal is reduced to hydroxyl groups with the liberation of hydrogen peroxide ... 

The experimental evidence, first based on spectroscopic studies of coadsorption and later by STM, indicated that there was a good case to be made for transient oxygen states being able to open up a non-activated route for the oxidation of ammonia at Cu(110) and Cu(lll) surfaces. The theory group at the Technische Universiteit Eindhoven considered5 the energies associated with various elementary steps in ammonia oxidation using density functional calculations with a Cu(8,3) cluster as a computational model of the Cu(lll) surface. At a Cu(lll) surface, the barrier for activation is + 344 k.I mol 1, which is insurmountable copper has a nearly full d-band, which makes it difficult for it to accept electrons or to carry out N-H activation. Four steps were considered as possible pathways for the initial activation (dissociation) of ammonia (Table 5.1). 

Gold forms a continuous series of solid solutions with palladium, and there is no evidence for the existence of a miscibility gap. Also, the catalytic properties of the component metals are very different, and for these reasons the Pd-Au alloys have been popular in studies of the electronic factor in catalysis. The well-known paper by Couper and Eley (127) remains the most clearly defined example of a correlation between catalytic activity and the filling of d-band vacancies. The apparent activation energy for the ortho-parahydrogen conversion over Pd-Au wires wras constant on Pd and the Pd-rich alloys, but increased abruptly at 60% Au, at which composition d-band vacancies were considered to be just filled. Subsequently, Eley, with various collaborators, has studied a number of other reactions over the same alloy wires, e.g., formic acid decomposition 128), CO oxidation 129), and N20 decomposition ISO). These results, and the extent to which they support the d-band theory, have been reviewed by Eley (1). We shall confine our attention here to the chemisorption of oxygen and the decomposition of formic acid, winch have been studied on Pd-Au alloy films. 

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