Polyolefin is a major industry that is important for our economy and impacts every aspect of our lives. The discovery of new transition metal-based catalysts is one of the driving forces for the further advancement of this field. Whereas the classical heterogeneous Ziegler-Natta catalysts and homogeneous early transition metal metallocene catalysts remain the workhorses of the polyolefin industry, in roughly the last decade, tremendous progress has been made in developing non-metallocene-based olefin polymerization catalysts. Particularly, the discovery of late transition metal-based olefin polymerization catalysts heralds a new era for this field. These late transition metal complexes not only exhibit high activities rivaling their early metal counterparts, but more importantly they offer unique properties for polymer architectural control and copolymerization with polar olefins. In this book, the most recent major breakthroughs in the development of new olefin polymerization catalysts, including early metal metallocene and non-metallocene complexes and late transition metal complexes, are discussed by leading experts. The authors highlight the most important discoveries in catalysts and their applications in designing new polyolefin-based functional materials.

The design of efficient syntheses of medicinal agents is one of the prime goals of the process chemist in the pharmaceutical industry. The expanding list of metal-mediated reactions has had a major impact on this endeavor over the last two decades. This volume will highlight some of the areas of organometallic chemistry that have played a particularly important role in development. The chapters are written by chemists who work in the process groups of major pharmaceutical companies and fine chemical manufacturers. Having demonstrated the power of organometallics in their processes the authors herein expand upon their experiences with examples from the literature as reported by process groups within the industry. The chapters are organized either by the application of a particular metal or reaction class. Removal of the residual metal(s) from the isolated active pharmaceutical ingredient (API) is key to the release of the material for human consumption, and hence, is reviewed here as well. This volume of Topics in Organometallic Chemistry is presented to offer a representative cross section of organometallic applications in the pharmaceutical industry as well as to give an appreciation for the creativity possible in process chemistry.

It was only in the early 1990s that carbenes with the carbene carbon being incorporated in a nitrogen containing heterocycle (N-heterocyclic carbenes or NHCs) were found to be stable enough to be isolated. Since the first report on the application of NHCs as ligands in transition metal catalysis in 1995, NHC have found numerous applications and have been established as a versatile and indispensable class of ligands. For many reactions like metathesis or cross-coupling reactions NHCs have often become the ligands of choice, allowing otherwise difficult transformations. In this book leading experts have surveyed major areas of application of NHC metal complexes in catalysis. The authors have placed a special focus on nickel- and palladium-catalyzed reactions, on applications in metathesis reactions, on oxidation reactions and on the use of chiral NHC-based catalysts. This compilation is rounded out by an introductory chapter and a chapter dealing with synthetic routes to NHC metal complexes. The use of NHC as ligands in catalysis has reached a certain level of maturity and this book allows the reader to get a balanced view of this increasingly important ligand class.

A wide range of ?elds within supramolecular chemistry are of current and great interest ranging from nanosciences, medicinal sciences, biosciences, and even organic sciences and this is a mature and extremely active area of research. In 1978, Lehn de?ned this chemistry as the "chemistry of molecular assemblies and of the intermolecular bond." In other words, supramolecular chemistry is noncovalent chemistry based upon covalent chemistry. On the other hand, it is well known that replacing the carbon atom of cyclic compounds can lead to dramatic changes in chemical and physical properties and the principles of homocyclic chemistry are often of limited value and may even lead to incorrect results. This is often indeed the case in supramolecular chemistry. The modern explosion of nonochemistry is highly based upon the fundamental recognition of intermolecular interactions engendered by supramolecular scientists. In this volume entitled Heterocyclic Supramolecules I, a part of the series Topics in Heterocyclic Chemistry, some selected topics in noncovalent ch- istry from the last decade are highlighted, with attention particularly focused on heterocyclic supramolecules as well as heterocycle-based nanosciences. The ?rst chapter, "Molecular Recognition with designed Heterocycles and their Lanthanide Complexes" by S. Mameri, S. Shinoda, and H. Tsukube - scribes various synthetic receptors for speci?c binding of cationic anionic guests mainly in the solution states. Furthermore, special attention is directed at the heterocycle-lanthanide complexes that worked as luminescent sensory devices of biologically important anions. Thus, "rare" earth metals are making the change into "hopeful" earth metals.

Themodernbillion-dollardrug-discoveryprocessstronglyreliesonbothhi- throughput synthesis and screening methods. Whereas the latter is based on molecular biological methods, the ef?cient and reliable generation of c- pound collections often makes use of combinatorial chemistry. Discovered in the 1980s, this methodology was explored extensively in the 1990s by groups in academia and in industry. Without any doubt, combinatorial chemistry changed the whole drug-discovery process and found many applications in cropscience and the material sciences. However, since its implementation, solution- and solid-phase techniques have been competing with each other, and although many companies started theircombinatorialchemistryprogramwithsolid-phasetechniques, soluti- phase combinatorial methods have taken over and now account for appro- mately 25% of all combinatorial efforts. The syntheses of complex, non-polymeric structures, discovered in the 1960s by the late Bruce Merri?eld, was largely ignored in the context of solid supports, mainly due to the fact that appropriate synthesis techniques were not available. Since solid-phase chemical methodology strongly differs from traditional solution-phase chemistry, two chapters deal with this topic. The Brase group (Jung, Wiehn, Brase) gives an overview of multifunctional linkers, which can beusedforthegenerationofdiversity-orientedcollections, simplybycleavage fromresins. Still in its infancy, solid-phase reactions employ "simple" amide chemistry in most cases due to their high-yielding, reliable protocols. Ljungdahl, Br- ?eld, and Kann address solid-phase organometallic chemistry, which is now one ofthe great challenges in reliable solid-phase organicsynthesis."

Aldol Reactions provides a comprehensive up-to-date overview of aldol reactions including application of different metal enolates; catalytic aldol additions catalyzed by different Lewis acids and Lewis bases; enantioselective direct aldol additions; antibodies and enzyme catalyzed aldol additions and the recent aggressive development of organocatalyzed aldol additions.

The power of each method is demonstrated by several applications in total synthesis of natural products. The pros and cons of these methodologies with regard to stereoselectivity, regioselectivity and application in total synthesis of natural products are discussed. Great importance is set to the diverse possibilities of the manual of aldol reaction to install required configurations in complicated natural product synthesis.

Heterogeneous catalysis has been essential to the development of efficient chemical processes for more than a century, and this field has been traditionally part of the solid state chemistry and surface science communities. The design of better catalysts has raised the following questions: "what is the structure of the active sites?" and "how to control their nature?" The necessary need to develop more sustainable chemical processes and the success of homogeneous catalysis relying on molecular organometallic chemistry has led the community of molecular chemists to investigate the preparation of single-site heterogeneous catalysts. The authors discuss the molecular design, the preparation, the characterisation and the catalytic applications of well-defined oxides and metal particles. The readers will acquire a molecular understanding of heterogeneous catalysis, which will help them develop a critical view and which will attract them to study this fascinating field.

The use of phosphine derivatives has historically induced the tremendous development of catalysis (both non-asymmetric and asymmetric). Although the chemistry of amines is more documented, the use of nitrogen-containing ligands only appeared recently. Nevertheless, during the last ten years, the results describing chiral diamine preparations and their uses in asymmetric catalysis and synthesis are increasing faster than their phosphorus counterparts. The reader will find in this volume the most recent methods for the synthesis of chiral diamines as well as their applications in asymmetric catalysis of CC bond formation. Particular attention will be given to spartein and derivatives of such diamines. Recently, the particular properties and the chemistry of amines allowed to obtain catalysts easy to separate and recycle and new types of ligands such as diaminocarbenes, ureas and thioureas. Finally, the complexing properties of some diamines allowed the formation of complexes with chirality "at the metal " which is of major theoretical interest and presents numerous potential applications.

3.1.1 ?-Conjugated Materials ?-conjugated polymers (CPs) and oligomers are materials with an extended ?-system along the backbone. The materials possess many remarkable prop- ties, including high charge carrier mobilities, electrical conductivities (doped), electrochromism, and electroluminescence [1]. These properties have been taken advantage of in exploration of potential applications including in ch- ical sensors, light-emitting devices, and ?eld-effect transistors. Many efforts have been devoted to synthesizing new conjugated polymers and oligomers in an effort to increase their processibility, optimize the desirable properties, and explore new properties. In Fig. 3.1 are shown examples of some of the CPs that have been prepared and studied. Coupling ?-conjugated materials to metal complexes gives hybrid mate- als in which the properties of the metal complex may be coupled to those of the conjugated backbone [2]. For example, these materials could be used in energy-harvesting devices such as solar cells or polymer-based light-emitting devices,wherehighchargecarrier mobilities of theconjugatedmaterialmay be combined with either the light-absorbing or emitting metal groups, giving improved device performance [3, 4]. In addition to an electronic role, metal complexes may also be used to geometrically orient ?-conjugated materials in speci?c three-dimensional arrangments in the solid state. Careful conside- tion of theelectronicinteractionsand excitedstatesisnecessary for thedesign of functional materials of this type.

Directed metalation is recognized as one of the most useful methodologies for the regio- and stereoselective generation of organometallic species, the generation of which necessarily leads to the selective formation of organic products. Cyclometalation using Li, Mn, and Pd, and directed hydrometalation and carbometalation using Al and Zn, have been utilized for regio- and/or stereoselective synthesis for decades. Recently, a new chelation-assisted methodology has been developed not only for controlling regio- and stereoselectivity of reactions, but also for accelerating reactions. In particular, chelation-methodology has been utilized as a new activation method, in which a carbon-metal bond is generated directly from a C-H bond; a reaction rarely achieved using conventional methods. A wide variety of catalytic functionalization reactions of C-H bonds by the utilization of a chelation, have been developed recently and are comprehensively discussed in this book by leading experts. In addition, new approaches to directed hydrometalation and directed carbometalation as a key step are also discussed. A unique stereo- and regioselective hydroformylation has been developed through the utilization of directed hydrometalation. The regioselective Mizoroki-Heck reaction is another example in which directed carbometalation can be used to achieve a high regioselectivity. These examples emphasize how these innovative methodologies are contributing to different fields of chemistry.

Hydrotreating catalysis with transition metal sulphides is one of the most important areas of industrial heterogeneous catalysis. The present book deals with the chemical and catalytic aspects of transition metal sulphides, focusing on their use in hydrotreating catalysis. The book?'s 12 chapters present reviews of solid-state, coordination and organometallic chemistry, surface science and spectroscopic studies, quantum chemical calculations, catalytic studies with model and real catalysts, as well as refinery processes. A presentation of state-of-the-art background to pertinent work in the field. Can be used as an introduction to the chemical and catalytic properties of transition metal sulphides as well as an advanced level reference.

About eight years ago, the catalytic carbonylation of organic nitro compounds was a research field developed enough to justify a rather long review on this subject. Now, we feel that the scientific results and new achievements in this field, very important even from an industrial point of view, require a book in order to be adequately presented. The competition between the catalytic carbonylation of organic nitro compounds and other chemical routes for the synthesis of a variety of organic compounds has not yet come to an end, but many progresses have been done in the former field. We also like to emphasize that this type of research does not only involve relevant industrial problems to be solved, but it opens a research field where the academic interests (mechanism of the reactions, isolation of the intermediates in the catalytic cycles, synthesis of model compounds and so on) can find a lot of opportunities.

For fifty years, Hydrosilylation has been one of the most fundamental and elegant methods for the laboratory and industrial synthesis of organosilicon and silicon related compounds. Despite the intensive research and continued interest generated by organosilicon compounds, no comprehensive book incorporating its various aspects has been published this century.

The aim of this book is to comprehensively review the advances of hydrosilylation processes since 1990. The survey of the literature published over the last two decades enables the authors to discuss the most recent aspects of hydrosilylation advances (catalytic and synthetic) and to elucidate the reaction mechanism for the given catalyst used and the reaction utilization. New catalytic pathways under optimum conditions necessary for efficient synthesis of organosilicon compounds are presented. This monograph shows the extensive development in the application of hydrosilylation in organic and asymmetric syntheses and in polymer and material science.

This series presents critical reviews of the present position and future trends in modern chemical research. It contains short and concise reports on chemistry, each written by a world renowned expert. This publication is still valid and useful after five or ten years. Scientists and practitioners in the mentioned fields and in industry will benefit from this series. Further information as well as the electronic version of the whole content is available at: springerlink.com

Eighty per cent of all compounds produced in the chemical and pharmaceutical industries require at least one essential catalytic step during their synthesis. At the same time the use of hydrocarbons as a feed-stock for commodity and fine chemicals typically requires an oxidation step, which is usually mediated by a transition metal compound. Consequently oxidation catalysis is a major research field in chemistry, both in academia and in industry. In many such processes, species with metal-carbon bonds are formed as key intermediates, and these processes represent the primary focus of this volume. An important aspect covered by some of the expert contributors is the use of organic ligands - and thus organometallic complex metal fragments - to achieve efficient oxidation catalysis. It has not been self-evident that organometallic complexes can survive the conditions necessary for polar oxygen-transfer reactions, but research over the last decade concerning oxo and peroxo complexes functionalized by organic ligands has clearly shown that relatively non-polar M-C bonds can be quite stable in the presence of oxidants and protic media, and that they may even be essential for the favourable activity and life-time of a catalyst. Also considered in this context is the oxidation chemistry of basic organometallic species in the gas phase, as this may reveal fundamental characteristics inherent to oxidation catalysts.

This book highlights cyclization via carbopalladation and acylpalladation and Heck-pericyclic sequences. They discuss p-allyl palladium-based cascade reactions, Michael-type additions as an entry to transition-metal-promoted cyclizative transformations, and sequential or consecutive palladium-catalyzed processes, and show Pauson-Khand cascades, metal-catalyzed cyclizations of acyclic precursors, as well as cascade and sequential ruthenium-catalyzed transformations. This is a comprehensive overview of an exciting and highly dynamic, and innovative methodological concept.

Control over macromolecular architecture and resulting material properties has been a central goal of polymer chemistry. There has been much interest in developing new synthetic routes to prepare smart materials with novel compositions and topologies for various applications. The considerable progress in the metal mediated macromolecular engineering over the past decade has had a major impact on the development of well-defined macromolecular architectures and the synthesis of smart materials. Particularly, remarkable strong developments have been observed for the synthesis of smart materials via four metal mediated macromolecular engineering techniques; Anionic, ROMP, ATRP and Click Chemistry. These materials have found uses in advanced microelectronics, technical and biomedical applications as well as in chemical sensors applications.

This book is comprised of 27 chapters written by leading scientists from NATO and Partner Countries who have greatly contributed in the area of Anionic, ROMP, ATRP and Click Chemistry. It highlights the fundamental aspects and recent developments of these four powerful techniques and evaluate their potential in the syntheses of smart materials from complex structures (grafts, brushes, dendrimers, etc.) to nanostructures (self-assembly, nano-size, etc) for a wide range of applications.

The book reports on the synthesis of a wide range of well-defined complex polymeric systems such as thermoresponsive smart polymers, star copolymers, biocompatible polymers, amphipilic smart nano structured, conducting polymers, self assembled polymers, and hyperbranced polymers.

Material synthesis by the transformation of organometallic compounds (precursors) by vapor deposition techniques such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) has been in the forefront of modern day research and development of new materials. There exists a need for new routes for designing and synthesizing new precursors as well as the application of established molecular precursors to derive tuneable materials for technological demands. With regard to the precursor chemistry, a most detailed understanding of the mechanistic complexity of materials formation from molecular precursors is very important for further development of new processes and advanced materials. To emphasize and stimulate research in these areas, this volume comprises a selection of case studies covering various key-aspects of the interplay of precursor chemistry with the process conditions of materials formation, particularly looking at the similarities and differences of CVD, ALD and nanoparticle synthesis, e.g. colloid chemistry, involving tailored molecular precursors.

Broad, comparative coverage of hypervalent compounds —a much-needed foundation in a rapidly growing field of chemistry.

Although hypervalency is already a mature field in chemistry, it has seen a new surge of interest in recent years due to the discovery of compounds useful in organic synthesis, as well as others with significant applications for materials science.

Now, this comprehensive book—written by a group of twenty leading experts in the field—provides an authoritative blueprint on the subject. Instead of focusing on compounds specific to one element, it presents a review of structure and reactivity among an extensive array of main group, organic, and organometallic hypervalent compounds. In so doing, the book offers essential information on underlying principles that unify seemingly unrelated families of main group element compounds.

An invaluable resource for both organic and inorganic chemists, Chemistry of Hypervalent Compounds includes:

• An overview of general aspects of structure and reactivity common among hypervalent compounds
• Information on such recently characterized organic compounds as silicon, phosphorus, sulfur, iodine, and xenon
• A review of new organometallic compounds with synthetic applications
• Solid background material on compounds important in advanced materials science, such as semiconductors
• A systematic approach using the N-X-L designation, where N represents the valence electrons of the central atom X, and L the ligands that bond the compound.

Inorganic Chemistry This series reflects the breadth of modern research in inorganic chemistry and fulfils the need for advanced texts. The series covers the whole range of inorganic and physical chemistry, solid state chemistry, coordination chemistry, main group chemistry and bioinorganic chemistry. Synthesis of Organometallic Compounds A Practical Guide Edited by Sanshiro Komiya Tokyo University of Agriculture and Technology, Japan. This book describes the concepts of organometallic chemistry and provides an overview of the chemistry of each metal including the synthesis and handling of its important organometallic compounds. Synthesis of Organometallic Compounds: A Practical Guide provides:
* an excellent introduction to organometallic synthesis
* detailed synthetic protocols for the most important organometallic syntheses
* an overview of the reactivity, applications and versatility of organometallic compounds
* a survey of metals and their organometallic derivatives
The purpose of this book is to serve as a practical guide to understanding the general concepts of organometallics for graduate students and scientists who are not necessarily specialists in organometallic chemistry.

Inorganic and Organometallic Reaction Mechanisms Second Edition Jim D. Atwood Inorganic and Organometallic Reaction Mechanisms, Second Edition covers both classic inorganic reaction mechanisms and organometallic reaction mechanisms. Introductions are provided for each group of reaction mechanisms, and extensive problems (many with references) are offered at the end of each chapter, as are summaries that provide students with thoughtful overviews. In this new edition, references have been updated and new problems have been added to each chapter. Information on NMR techniques and other newer techniques, such as time-resolved infrared spectroscopy, has been added to the chapter on chemical kinetics. The chapter describing ligand substitution reactions on square planar complexes now includes a section on dissociative reactions of square-planar complexes. Significant material on reactions of seventeen electron complexes has been added to the coverage of organometallic substitution reactions, while the material on oxidative-addition and reductive-elimination reactions has been extensively rewritten. The chapter on inorganic electron transfer through inner and outer sphere mechanisms has been augmented by a substantial section on organometallic electron transfer. This book is intended for advanced undergraduate and graduate students and instructors in inorganic and organometallic chemistry. It will also be a useful tutorial for organic chemists who use organometallic reagents for syntheses. Also available Kinetics and Mechanism of Reactions of Transition Metal Complexes Second, Thoroughly Revised Edition R.G. Wilkins Hardcover. Softcover. Organometallics: A Concise Introduction Second, RevisedEdition Ch. Elschenbroich and A. Salzer Hardcover. Softcover. Transition Metal Chemistry: The Valence Shell in d-Block Chemistry M. Gerloch and E.C. Constable Hardcover. Softcover. Electron Transfer and Radical Processes in Transition-Metal Chemistry D. Astruc Hardcover.

A comprehensive discussion of the theory, practice and application of catalytically active transition metal species and their application in the production of specialist polymeric materials. The material is presented in a progressive manner, suitable for non-experts and those seeking an introduction to the field. The bibliographies supplied are complete and up to date, making the book an indispensable guide to the primary literature for the more theoretical background to the topics discussed.
After a comprehensive discussion of initiating systems for speciality chemical synthesis the book goes on to deal with a wide range of topics in materials science, including: alkenamers, polyacetylenes, industrial applications and liquid rocket engine fuels.

In the last decade there have been numerous advances in the area of rhodium-catalyzed hydroformylation, such as highly selective catalysts of industrial importance, new insights into mechanisms of the reaction, very selective asymmetric catalysts, in situ characterization and application to organic synthesis. The views on hydroformylation which still prevail in the current textbooks have become obsolete in several respects. Therefore, it was felt timely to collect these advances in a book.

The book contains a series of chapters discussing several rhodium systems arranged according to ligand type, including asymmetric ligands, a chapter on applications in organic chemistry, a chapter on modern processes and separations, and a chapter on catalyst preparation and laboratory techniques. This book concentrates on highlights, rather than a concise review mentioning all articles in just one line. The book aims at an audience of advanced students, experts in the field, and scientists from related fields. The didactic approach also makes it useful as a guide for an advanced course.

Provides vital information on organometallic compounds, their preparation, and use in synthesis, and explores the fundamentals of the field and its modern applications Fully updated and expanded to reflect recent advances, the new, seventh edition of this bestselling text presents students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications. Increased focus is given to organic synthesis applications, nanoparticle science, and green chemistry. This edition features up-to-date examples of fundamental reaction steps and greater emphasis on key topics like oxidation catalysis, CH functionalization, nanoclusters and nanoparticles, and green chemistry. New coverage is added for computational chemistry, energy production, and biochemical aspects of organometallic chemistry. The Organometallic Chemistry of the Transition Metals, Seventh Edition provides new/enhanced chapter coverage of ligand-assisted additions and eliminations; proton-coupled electron transfer; surface, supported, and cooperative catalysis; green, energy, and materials applications; and photoredox catalysis. It covers coordination chemistry; alkyls and hydrides; Pi-complexes; and oxidative addition and reductive elimination. The book also features sections on insertion and elimination; spectroscopy; metathesis polymerization and bond activation; and more. Provides an excellent foundation of the fundamentals of organometallic chemistry Includes end-of-chapter problems and their solutions Expands and includes up-to-date examples of fundamental reaction steps and focuses on important topics such as oxidation catalysis, CH functionalization, nanoparticles, and green chemistry Features all new coverage for computational chemistry, energy production, and biochemical aspects of organometallic chemistry The Organometallic Chemistry of the Transition Metals, Seventh Edition is an insightful book that will appeal to all advanced undergraduate and graduate students in organic chemistry, organometallic chemistry, inorganic chemistry, and bioinorganic chemistry, as well as any practicing chemist in those fields.

Das Buch bietet die wichtigsten Darstellungsmethoden, Strukturen und Reaktionstypen der Organometallchemie. Um die Dynamik des Gebietes zu vermitteln, werden an diversen Stellen Forschungsergebnisse aus jungster Zeit vorgestellt. Statt der Prasentation einer Vielzahl von Einzelfakten wird das Verstandnis der Triebkraft metallorganischer Reaktionen und des Zusammenhanges zwischen Elektronenstruktur und Molekulbau angestrebt. Das Buch eignet sich als begleitender Text fur eine zweisemestrige Vorlesung wie sie vielerorts angeboten wird. Die Neuauflage enthalt zahlreiche Korrekturen und inhaltliche Aktualisierungen.