Oxidation metal complexes

Saturated metal complexes, oxidation states, and coordination numbers... 

Using IrClj Large number of metal complex oxidants or reductants Using cyt-c as partner Using Co(edta)" as partner Refs, below... 

Influence of Solubility and Structure on the Activity of Metal Complex Oxidation Catalysts... 

Fig. 8.3 Warren R. Roper (born in 1938) studied chemistry at the University of Canterbury in Christchurch, New Zealand, and completed his Ph.D. in 1963 under the supervision of Cuthbert J. Wilkins. He then undertook postdoctoral research with James P. Collman at the University of North Carolina at Chapel Hill in the US, and returned to New Zealand as Lecturer in Chemistry at the University of Auckland in 1966. In 1984, he was appointed Professor of Chemistry at the University of Auckland and became Research Professor of Chemistry at the same institution in 1999. His research interests are widespread with the emphasis on synthetic and structural inorganic and organometallic chemistry. Special topics have been low oxidation state platinum group metal complexes, oxidative addition reactions, migratory insertion reactions, metal-carbon multiple bonds, metallabenzenoids and more recently compounds with bonds between platinum group metals and the main group elements boron, silicon, and tin. His achievements were recognized by the Royal Society of Chemistry through the Organometallic Chemistry Award and the Centenary Lectureship. He was elected a Fellow of the Royal Society of New Zealand and of the Royal Society London, and was awarded the degree Doctor of Science (honoris causa) by the University of Canterbury in 1999 (photo by courtesy from W. R. R.)...

Sherrington, D. C. Polymer-supported metal complex oxidation catalysts. Pure Appl. Chem. 1988, 60, 401-414. 

Zhang, Y.C., Kaneko. M., Uchida, K.. Mizusaki, J. and Tagawa, H. (2001) Solid electrolyte CO2 sensors with lithium-ion conductor and Li transition metal complex oxide as solid reference electrode./. Electrochem. Soc., 148 (8). H81-4. 

Polystyrene-based resins have been used widely as supports for metal complex catalysts and other reactive species. These polymers, however, have a drawback in their limited thermo-oxidative stability [1,2]. The scope for application is therefore restricted, particularly in polymer-supported transition metal complex oxidation catalysts [3]. Consequently there is a need for the development of polymer supports with a much higher intrinsic thermo-oxidative stability. Polybenzimidazoles and polyimides are likely candidates in this respect. 

Acknowledgments We dedicate this paper to the memory of Carl Ballhausen, a great scientist and a dear friend (Fig. 5). We note in closing that the B G model is providing a firm foundation for structure/reactivity correlations in our current work on oxo-metal complexes [oxidative... 

The perovskite-type catalysts (ref.l), other non noble metal complex oxides catalysts (ref.2), and mixed metal oxides catalysts (ref.3) have been studied in our laboratory. The various preparation techniques of catalysts (ref.4 and 5), the adsorption and thermal desorption of CO, C2H5 and O2 (ref.6 and 7), the reactivity of lattice oxygen (ref.8), the electric conductance of catalysts (ref.9), the pattern of poisoning by SO2 (ref. 10 and 11), the improvement of crushing strength of support (ref. 12) and determination of the activated surface of complex metal oxides (ref. 13) have also been reported. 

The most often cited compounds which add to metal complexes oxidatively are H2, HX, RCOX (X = halogen), R3SiH and RS02X. Further examples from the recent literature are surveyed in the following. 

Most simple heteroles are liquids or viscous oils that can be Kugelrohr distilled under reduced pressure. Many of the solid heteroles are isolated by sublimation. Physical property data for a few of the simple compounds are included in Table 5. Quaternary salts, metal complexes, oxides, and sulfides tend to be crystalline solids with definite melting points. 

Recently Miyaura and co-workers have reported a trans-hydroboration of terminal alkynes using [Rh(COD)Cl]2[PCPr)3]4 or [Ir(COD)Cl]2[P( Pr)3]4 (eq 13). Mechanistic studies via deuteriumlabeling show that after the oxidative addition of the alkyne to the metal, the acetylenic deuterium undergoes migration to the S-carbon resulting in the formation of a vinylidene metal complex. Oxidative addition of borane to the metal complex and 1,2-... 

SELF-ASSEMBLY OF MONO- AND DINUCLEAR METAL COMPLEXES OXIDATION CATALYSIS AND METALLOENZYME MODELS... 

When a molecule diffuses near a metal surface, it is first physisorbed, i.e. it binds weakly to the surface without dissociation. The forces involved are of the Van der Waals type, i.e. weaker than 20 kJ-mol. This step is reversible, and desorption can rapidly occur. With H2, for instance, one can compare this with the formation of an H2 complex at the vacant metal site of a 16e metal complex. Oxidative addition may eventually occur at the surface (depending on the nature of the metal). In the case of the monometallic complex, the H2 complex can be stable and isolable (i.e. more strongly bonded to the metal than when physisorbed on a metal surface), or alternatively, it can be transient and rapidly form the metal-dihydride by oxidative addition. The difference is that, on the surface, the oxidative addition is bimetallic whereas, in organometallic chemistry, it is usually (but not always) monometallic ... 

Oxd = metal complex oxidizing agent. Red = reduced form of metal complex. Sub = non-metallic reducing substrate, Int = Intermediate, a free radical if Oxd is a one-equivalent oxidant. Oxd-Sub = complex between oxidizing agent and reductant. Reaction by this route does not involve the formation of free radicals or other relatively high-energy intermediates... 

Most of the neutral bis-arene metal complexes oxidize readily in air to give bis-arene cations. As would be expected, the bis-arene cations are more resistant to oxidative decomposition than the neutral analogues and, in weakly alkaline solutions, [ r-C6H<)2Cr] may be kept in air for several weeks. 

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