Advances in Catalytic Activation of Dioxygen by Metal Complexes

ISBN-13: 9781441952387 / Angielski / Miękka / 2010 / 338 str.

Laszlo I. Simandi

Opis

The subject of dioxygen activation and homogeneous catalytic oxidation by metal complexes has been in the focus of attention over the last 20 years. The widespread interest is illustrated by its recurring presence among the sessions and subject areas of important international conferences on various aspects of bioinorganic and coordination chemistry as well as catalysis. The most prominent examples are ICCC, ICBIC, EUROBIC, ISHC, and of course the ADHOC series of meetings focusing on the subject itself. Similarly, the number of original and review papers devoted to various aspects of dioxygen activation are on the rise. This trend is due obviously to the relevance of catalytic oxidation to biological processes such as dioxygen transport, and the action of oxygenase and oxidase enzymes related to metabolism. The structural and functional modeling of metalloenzymes, particularly of those containing iron and copper, by means of low-molecular complexes of iron, copper, ruthenium, cobalt, manganese, etc., have provided a wealth of indirect information helping to understand how the active centers of metalloenzymes may operate. The knowledge gained from the study of metalloenzyme models is also applicable in the design of transition metal complexes as catalytsts for specific reactions. This approach has come to be known as biomimetic or bioinspired catalysis and continues to be a fruitful and expanding area of research.

Recenzje

"Three of these topics focus heavily on biomimetic oxidations and how they might be applied to catalysis of organic compounds. Each is very well written and the material is thoroughly reviewed. It will be of great interest to the specialist in catalytic oxidation and in particular to those interested in liquid phase oxidation. The authors have long experience in the fields that are reviewed so the work is timely, balanced and presented in depth."
(James E. Lyons, The Catalyst Group, Spring House, PA (2003)

Spis treści

1: Catalytic oxidations using ruthenium porphyrins; M.B. Ezhova, B.R. James. 1. Introduction: oxygenase and oxidase activity. 2. Reactions of ruthenium porphyrin complexes with O2 and other oxidants. 3. Oxidation of organic substrates. 4. Conclusions. 5. Abbreviations. 6. References. 2: Copper-dioxygen complexes and their roles in biomimetic oxidation reactions; C. Xin Zhang, Hong-Chang Liang, K.J. Humphreys, K.D. Karlin. 1. Introduction. 2. Copper-dioxygen adducts. 3. Copper oxygenase chemistry. 4. Copper oxidase models: catalytic alcohol oxidation. 5. Copper-phenanthroline DNA oxidation. 6. References. 3: Catalytic oxidations of alcohols. R.A. Sheldon, I.W.C.E. Arends. 1. Introduction. 2. Mechanisms. 3. Ruthenium-catalysed oxidations with O2. 4. Palladium- catalysed oxidations with O2. 5. Copper- catalysed oxidations with O2. 6. Other metals as catalysts for oxidation with O2. 7. Catalytic oxidation of alcohols with hydrogen peroxide and alkyl hydroperoxides. 8. Concluding remarks. 9. references. 4: Functional model oxygenations by nonheme iron complexes. T. Funabiki. 1. Introduction. 2. heme and nonheme oxygenases. 3. Functional model studies on nonheme iron. 4. Functional model systems for nonheme iron monooxygenases. 5. from functional model to catalysis. 6. References. 5: Catalysis for selective aerobic oxidation under ambient conditions. E. Boring, Y.V. Geletti, C.L. Hill. 1. Introduction. 2. Discovery of Au(III)Cl2NO3(thioether)/O2 catalytic oxidation system. 3. Stoichiometric Au(III) reduction by thioethers. 4. In situ catalyst preparation. 5. Reaction stoichiometry. 6. Empirical reaction rate law. 7. Rate limiting step. 8. proposed reaction mechanism. 9. Mechanisms ruled out. 10. Origin of oxygen in sulfoxide product: role of H2O2 in sulfoxidation. 11. Reoxidation of Au(I) by dioxygen. Catalyst preparation from Au(I) complex. 12. Effect of ligands on reactivity. 13. Product inhibition (DMSO) effect. 14. Co-catalysis by transition metal ions. 15. Solvent effects. 16. Heterogeneous systems. 17. Effect of amino acids. 18. Oxidation of thioethers other than CEEs. 19. Experimental details. 20. Conclusions. 6: Catalytic oxidations using cobalt(II) complexes; L.I. Simándi. 1. Introduction. 2. Cobalt dioxygen complexes. 3. Oxidations catalyzed by Co(salen) complexes. 4. Oxidations catalyzed by cobaloximes. 5. Oxidations catalyzed by cobalt(II) porphyrins. 6. Oxidation weith cobalt(II) phthalocyanines. 7. Oxidations catalyzed by cobalt(II) pyridine complexes. 9. Cobalt-Fenton systems. 10. Co(acac)2 catalyzed oxidations. 11.