This monograph consists of the proceedings of the Fifth International Symposium on the Activation of Dioxygen and Homogeneous Catalytic Oxidation, held in College Station, Texas, March 14-19, 1993. It contains an introductory chapter authored by Professors D. H. R. Barton and D. T. Sawyer, and twenty-nine chapters describing presentations by the plenary lecturers and invited speakers. One of the invited speakers, who could not submit a manuscript for reasons beyond his control, is represented by an abstract of his lecture. Also included are abstracts of forty-seven posters contributed by participants in the symposium. Readers who may wish to know more about the subjects presented in abstract form are invited to communicate directly with the authors of the abstracts. This is the fifth international symposium that has been held on this subject. The first was hosted by the CNRS, May 21-29, 1979, in Bendor, France (on the Island of Bandol). The second meeting was organized as a NATO workshop in Padova, Italy, June 24-27, 1984. This was followed by a meeting in Tsukuba, Japan, July 12-16, 1987. The fourth symposium was held at Balatonfured, Hungary, September 10-14, 1990. The sixth meeting is scheduled to take place in Delft, The Netherlands (late Spring, 1996); the organizer and host will be Professor R. A. Sheldon.

Dioxygen activation is a rapidly developing field in which research is directed at (1) modelling of biological oxidations, (2) design and utilization of new catalysts for oxidative transformations of organic substrates, (3) application of O 2 (and H 2 O 2 ) as a cheap oxidant in the manufacture of fine and bulk chemicals. Provided here is a collection of both review and original papers covering all aspects of dioxygen activation. All papers provide background information of previous work. Reactions mechanisms are extensively treated and a keyword index facilitates quick orientation. The book should prove invaluable to organic, bioinorganic and coordination chemists as well as biochemists interested in homogeneous catalysis.

The activation of dioxygen by metal ions has both synthetic potential and biological relevance. Dioxygen is the cleanest oxidant for use in emission-free technologies to minimize pollution of the environment. The book gives a survey of those catalyst systems based on metal complexes which have been discovered and studied in the last decade. They activate molecular oxygen and effect the oxidation of various organic compounds under mild conditions. Much of the recent progress is due to a search for biomimetic catalysts that would duplicate the action of metalloenzymes. Mechanistic aspects are emphasized throughout the book. An introductonary chapter reviews the chemistry of transition metal dioxygen complexes, which are usually the active intermediates in the catalytic reactions discussed. Separate chapters are devoted to oxidation of saturated, unsaturated and aromatic hydrocarbons, phenols, catechols, oxo-compounds, phosphorus, sulfur and nitrogen compounds.

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.

hemistry is the science about breaking and forming of bonds between atoms. One of the most important processes for organic chemistry is breaking bonds C–H, as well as C–C in various compounds, and primarily, in hydrocarbons. Among hydrocarbons, saturated hydrocarbons, alkanes (methane, ethane, propane, hexane etc. ), are especially attractive as substrates for chemical transformations. This is because, on the one hand, alkanes are the main constituents of oil and natural gas, and consequently are the principal feedstocks for chemical industry. On the other hand, these substances are known to be the less reactive organic compounds. Saturated hydrocarbons may be called the “noble gases of organic chemistry” and, if so, the first representative of their family – methane – may be compared with extremely inert helium. As in all comparisons, this parallel between noble gases and alkanes is not fully accurate. Indeed the transformations of alkanes, including methane, have been known for a long time. These reactions involve the interaction with molecular oxygen from air (burning – the main source of energy!), as well as some mutual interconversions of saturated and unsaturated hydrocarbons. However, all these transformations occur at elevated temperatures (higher than 300–500 °C) and are usually characterized by a lack of selectivity. The conversion of alkanes into carbon dioxide and water during burning is an extremely valuable process – but not from a chemist viewpoint.

Sets the stage for environmentally friendly industrial organic syntheses From basic principles to new and emerging industrial applications, this book offers comprehensive coverage of heterogeneous liquid-phase selective oxidation catalysis. It fully examines the synthesis, characterization, and application of catalytic materials for environmentally friendly organic syntheses. Readers will find coverage of all the important classes of catalysts, with an emphasis on their stability and reusability. Liquid Phase Oxidation via Heterogeneous Catalysis features contributions from an international team of leading chemists representing both industry and academia. The book begins with a chapter on environmentally benign oxidants and then covers: Selective oxidations catalyzed by TS-1 and other metal-substituted zeolites Selective catalytic oxidation over ordered nanoporous metallo-aluminophosphates Selective oxidations catalyzed by mesoporous metal-silicates Liquid phase oxidation of organic compounds by supported metal-based catalysts Selective liquid phase oxidations in the presence of supported polyoxometalates Selective oxidations catalyzed by supported metal complexes Liquid phase oxidation of organic compounds by metal-organic frameworks Heterogeneous photocatalysis for selective oxidations with molecular oxygen All the chapters dedicated to specific types of catalysts follow a similar organization and structure, making it easy to compare the advantages and disadvantages of different catalysts. The final chapter examines the latest industrial applications, such as the production of catechol and hydroquinone, cyclohexanone oxime, and propylene oxide. With its unique focus on liquid phase heterogeneous oxidation catalysis, this book enables researchers in organic synthesis and oxidation catalysis to explore and develop promising new catalytic materials and synthetic routes for a broad range of industrial applications.

Taking an interdisciplinary approach, this book and its counterpart, Active Oxygen in Biochemistry, explore the active research area of the chemistry and biochemistry of oxygen. Complementary but independent, the two volumes integrate subject areas including medicine, biology, chemistry, engineering, and environmental studies.

This book consists of lectures presented by international authorities in the field, at a course on Oxidation Catalysis organized by the Dutch Research School in Catalysis at Rolduc in June 1994.The material covered spans the whole range of the subject from the fundamental principles of gas and liquid phase oxidations to reactor engineering for industrial processing. The use of catalytic oxidation in both bulk and fine chemicals manufacture and the different types of catalysis — heterogeneous-gas phase, homogeneous-liquid phase and heterogeneous-liquid phase — are discussed. In addition, a few special topics, such as electrocatalytic and high-temperature oxidation are dealt with.The book is intended for graduate students or industrial researchers who wish to acquaint themselves with the underlying principles of catalytic oxidations and the numerous applications of this important technology.

The first book to place recent academic developments within the context of real life industrial applications, this is a timely overview of the field of aerobic oxidation reactions in the liquid phase that also illuminates the key challenges that lie ahead. As such, it covers both homogeneous as well as heterogeneous chemocatalysis and biocatalysis, along with examples taken from various industries: bulk chemicals and monomers, specialty chemicals, flavors and fragrances, vitamins, and pharmaceuticals. One chapter is devoted to reactor concepts and engineering aspects of these methods, while another deals with the relevance of aerobic oxidation catalysis for the conversion of renewable feedstock. With chapters written by a team of academic and industrial researchers, this is a valuable reference for synthetic and catalytic chemists at universities as well as those working in the pharmaceutical and fine chemical industries seeking a better understanding of these reactions and how to design large scale processes based on this technology.