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Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn

X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper

X-ray photoelectron spectroscopic studies of iron oxides

Surface studies of supported model catalysts

The chemistry of copper is extremely rich because it can easily access Cu0, CuI, CuII, and CuIII oxidation states allowing it to act through one-electron or two-electron processes. As a result, both radical pathways and powerful two-electron bond forming pathways via organmetallic intermediates, similar to those of palladium, can occur. In addition, the different oxidation states of copper associate well with a large number of different functional groups via Lewis acid interactions or π-coordination. In total, these feature confer a remarkably broad range of activities allowing copper to catalyze the oxidation and oxidative union of many substrates.

Oxygen is a highly atom economical, environmentally benign, and abundant oxidant, which makes it ideal in many ways.1 The high activation energies in the reactions of oxygen require that catalysts be employed.2 In combination with molecular oxygen, the chemistry of copper catalysis increases exponentially since oxygen can act as either a sink for electrons (oxidase activity) and/or as a source of oxygen atoms that are incorporated into the product (oxygenase activity). The oxidation of copper with oxygen is a facile process allowing catalytic turnover in net oxidative processes and ready access to the higher CuIII oxidation state, which enables a range of powerful transformations including two-electron reductive elimination to CuI. Molecular oxygen is also not hampered by toxic byproducts, being either reduced to water, occasionally via H2O2 (oxidase activity) or incorporated into the target structure with high atom economy (oxygenase activity). Such oxidations using oxygen or air (21% oxygen) have been employed safely in numerous commodity chemical continuous and batch processes.3

However, batch reactors employing volatile hydrocarbon solvents require that oxygen concentrations be kept low in the head space (typically <5–11%) to avoid flammable mixtures, which can limit the oxygen concentration in the reaction mixture.4,5,6 A number of alternate approaches have been developed allowing oxidation chemistry to be used safely across a broader array of conditions. For example, use of carbon dioxide instead of nitrogen as a diluent leads to reduced flammability.5 Alternately, water can be added to moderate the flammability allowing even pure oxygen to be employed.6 New reactor designs also allow pure oxygen to be used instead of diluted oxygen by maintaining gas bubbles in the solvent, which greatly improves reaction rates and prevents the build up of higher concentrations of oxygen in the head space.4a,7 Supercritical carbon dioxide has been found to be advantageous as a solvent due its chemical inertness towards oxidizing agents and its complete miscibility with oxygen or air over a wide range of temperatures.8 An number of flow technologies9 including flow reactors,10 capillary flow reactors,11 microchannel/microstructure structure reactors,12 and membrane reactors13 limit the amount of or afford separation of hydrocarbon/oxygen vapor phase thereby reducing the potential for explosions.

Enzymatic oxidizing systems based upon copper that exploit the many advantages and unique aspects of copper as a catalyst and oxygen as an oxidant as described in the preceding paragraphs are well known. They represent a powerful set of catalysts able to direct beautiful redox chemistry in a highly site-selective and stereoselective manner on simple as well as highly functionalized molecules. This ability has inspired organic chemists to discover small molecule catalysts that can emulate such processes. In addition, copper has been recognized as a powerful catalyst in several industrial processes (e.g. phenol polymerization, Glaser-Hay alkyne coupling) stimulating the study of the fundamental reaction steps and the organometallic copper intermediates. These studies have inspiried the development of nonenzymatic copper catalysts. For these reasons, the study of copper catalysis using molecular oxygen has undergone explosive growth, from 30 citations per year in the 1980s to over 300 citations per year in the 2000s.

A number of elegant reviews on the subject of catalytic copper oxidation chemistry have appeared. Most recently, reviews provide selected coverage of copper catalysts14 or a discussion of their use in the aerobic functionalization of C–H bonds.15 Other recent reviews cover copper and other metal catalysts with a range of oxidants, including oxygen, but several reaction types are not covered.16 Several other works provide a valuable overview of earlier efforts in the field.17 This review comprehensively covers copper catalyzed oxidation chemistry using oxygen as the oxidant up through 2011. Stoichiometric reactions with copper are discussed, as necessary, to put the development of the catalytic processes in context. Mixed metal systems utilizing copper, such as palladium catalyzed Wacker processes, are not included here. Decomposition reactions involving copper/oxygen and model systems of copper enzymes are not discussed exhaustively. To facilitate analysis of the reactions under discussion, the current mechanistic hypothesis is provided for each reaction. As our understanding of the basic chemical steps involving copper improve, it is expected that many of these mechanisms will evolve accordingly.

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Aerobic Copper-Catalyzed Organic Reactions

X-ray photoelectron spectroscopy of manganese—oxygen systems

X-ray photoelectron spectroscopic study of perovskite titanates and related compounds: An example of the effect of polarization on chemical shifts

Reactions of evaporated iron with O2 and H2O have been investigated by X-ray photoelectron spectroscopy. Binding energies of Fe2p3⁄2 and Ols electrons were measured during the course of reactions and their variation was discussed in terms of the positive and negative charges of the iron and oxygen of the surface oxide formed, respectively, assuming a simple charge-chemical shift relation. They are compared with the binding energies of the Ols in SiO2 Al2O3, Fe2O3, Cd(OH)2, KOH, and Ni(OH)2 and those of Fe2p3⁄2 in various iron compounds High reactivity of the surface oxide with H2O and the resulting hydroxyl group formation were observed. A rough estimation of the Fe to O atomic ratio of the surface oxide was also carried out from the ratio of the Fe and O peak areas.

X-Ray Photoelectron Spectroscopic Study for the Reaction of Evaporated Iron with O2 and H2O

X-ray photoelectron spectroscopic study of the reaction of evaporated metal films with chlorine gas

The core-electron binding energy obtained for small Pd clusters supported on various substrates is greater than that obtained for bulk Pd metal. The shifts of the core-electron binding energy and the core-valence-valence Auger-electron kinetic energy for small Pd clusters on the conductive amorphous carbon substrate are in good agreement with those calculated by the thermodynamic model using Miedema's semiempirical theory. Both experimentally and theoretically, the positive shift of the Pd core-electron binding energy with decreasing coverage is shown to be due to the photoemission initial-state effect. The shifts of the Pd core-electron binding energy with the coverage for small clusters on the semiconductive InSb and InP substrates are primarily due to the initial-state effect. The ratio of the photoemission initial-state-effect change to the photoemission final-state-effect change decreases with an increase of the polarizability of the substrate. The photoemission final-state effect predominantly arises from the positive shift of the Pd core-electron binding energy with decreasing coverage on the insulating ${\mathrm{SiO}}_{2}$ and ${\mathrm{Al}}_{2}$${\mathrm{O}}_{3}$ substrates. The changes in the terms of the extra-atomic relaxation energy for the Pd core hole and the potential energy of the Pd core electron differ for each substrate. The change in the extra-atomic relaxation energy for the Pd core hole varies with the change of the polarizability of the substrate. The change in the potential energy of the Pd core electron correlates with the difference in electronegativities of the substrate components.

Shigero Ikeda

Papers

X-ray photoelectron spectroscopy of manganese—oxygen systems

X-ray photoelectron spectroscopic study of perovskite titanates and related compounds: An example of the effect of polarization on chemical shifts

X-Ray Photoelectron Spectroscopic Study for the Reaction of Evaporated Iron with O2 and H2O

X-ray photoelectron spectroscopic study of the reaction of evaporated metal films with chlorine gas

Photoemission from small palladium clusters supported on various substrates