Advances in Catalytic Activation of Dioxygen by Metal Complexes

The catalytic activation of dioxygen continues to attract interest both due to its biological importance and synthetic potential. Metalloenzymes play crucial roles in metabolism by living organisms. The modelling of metalloenzymes by biomimetic metal complexes helps the search for useful oxidation catalysts and the understanding of their mechanisms of operation. Dioxygen is also the oxidant of choice in emission-free technologies aimed at minimising pollution of the environment, in line with the green chemistry requirements. This volume is devoted to recent progress in the field of catalytic oxidations using ruthenium, copper, iron, gold, cobalt and other complexes. Products and mechanistic aspects are given special emphasis throughout the book.

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. Oxidations via alkylperoxocobalt complexes. 12. Oxidations with co-cyclidine complexes. 13. Oxidations with cobalt peptide complexes. 15.Carboxylatocobalt complexes and salts. 16. Miscellaneous cobalt catalysts. 17. Conclusions. 18. References.