Organometallic chemistry is based on the reactions and use of a class of compounds (R-M) that contain a covalent bond between carbon and metal. They are prepared either by direct reaction of the metal with an organic compound or by replacement of a metal from another organometallic substance. Research in organometallic chemistry is also conducted in the areas of cluster synthesis, main-group derivatives in unusual oxidation states, organometallic polymers, unstable organometallic compounds and intermediates in matrices, structure determination of organometallic compounds in the solid state [X-ray diffraction] and gaseous states [electron diffraction], and mechanisms of reactions of transient silylenes and related species. In addition to the traditional metals and semimetals, elements such as selenium, lithium and magnesium are considered to form organometallic compounds, e.g. organomagnesium compounds MeMgI, iodo(methyl)magnesium and diethylmagnesium which are Grignard reagents an organo-lithium compound BuLi butyllithium; Organometallic compounds often find practical use as catalysts, the processing of petroleum products and the production of organic polymers.

Metal carbene complexes have made their way from organometallic curiosities to valuable reagents and catalysts. They offer novel synthetic opportunities in carbon carbon bond formation based on either carbene-centered reactions or on metal-templated processes which makes them indispensable in modern synthetic methodology. The most prominent metal carbenes are now either commercially available or easy to synthesize and handle by modern laboratory techniques. This volume organized in eight chapters written by the leading scientists in the field illustrates the theoretical background, non-classical nucleophilic and cycloaddition patterns, chromium-templated benzannulation and photo-induced reactions, rhodium-catalyzed carbene transfer as well as the principles and applications of olefin metathesis which coined the progress in synthetic methodology over the past decade. Designed for researchers in academia and industry as well as graduate students it presents the state-of-the-art potential of carbene complexes in modern organic synthesis.

Metal-arene pi-complexes show a rich and varied chemistry. The metal adds a third dimension to the planar aromatic compounds and coordination of a metal to an arene thus not only altering the reactivity of ring-carbons and substituents but also makes possible reactions that lead to chiral non-racemic products. This book, organized in nine chapters and written by leading scientists in the field provides the reader with an up-to-date treatise on the subject organized according to reaction type and use. It covers the wide spectrum of arene activation: from the electrophilic activation of h6-bound arene by pi-Lewis acid metal complex fragments, to reactions of nucleophilic h2-coordinated arene complexes. The preparation of complexes is detailed, as are the scope, limitations and challenges of reactions in contemporary pi-arene metal chemistry with special attention given to asymmetric transformations. The emphasis of the book is on transformations of interest to organic synthesis and on the use of the complexes as catalysts or as chiral ligands.
The book is written for academic and industrial researchers in organic, organometallic, and inorganic chemistry as well as for advanced chemistry students.

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.

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.

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.

 Organolithium chemistry occupies a central position in the selective construction of C-C bonds in both simple and complex molecules. Paralleling the surge of interest in methods for asymmetric synthesis, the use of organolithiums in enantioselective synthesis has witnessed spectacular advances in a little over a decade. This volume is the first dedicated to a comprehensive coverage of this important area. It is designed to provide graduate students and researchers with a rich source of essential information on synthesising molecules in an enantioselective manner using organolithiums, and be an inspiration for future developments. Following an overview chapter summarising the key milestones, successive chapters, each written by leading experts in their field, critically survey all the major areas of progress.

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.

In 1972, a very powerful catalytic cycle for carbon-carbon bond formation was 2 first discovered by the coupling reaction of Grignard reagents at the sp -carbon. Over the past 30 years, the protocol has been substantially improved and expanded to other coupling reactions of Li, B, N, O, Al, Si, P, S, Cu, Mn, Zn, In, Sn, and Hg compounds. These reactions provided an indispensable and simple methodology for preparative organic chemists. Due to the simplicity and rel- bility in the carbon-carbon, carbon-heteroatom, and carbon-metalloid bo- formations, as well as high efficiency of the catalytic process, the reactions have been widely employed by organic chemists in various fields. Application of the protocol ranges from various syntheses of complex natural products to the preparation of biologically relevant molecules including drugs, and of sup- molecules, and to functional materials. The reactions on solid surfaces allow robot synthesis and combinatorial synthesis. Now, many organic chemists do not hesitate to use transition metal complexes for the transformation of org- ic molecules. Indeed, innumerable organic syntheses have been realized by the catalyzed reactions of transition metal complexes that are not achievable by t- ditional synthetic methods. Among these, the metal-catalyzed cross-coupling reactions have undoubtedly contributed greatly to the development of such a new area of "metal-catalyzed organic syntheses." An excellent monograph for the cross-coupling reactions and other met- catalyzed C-C bond-forming reactions recently appeared in Metal-catalyzed Cross-coupling Reactions (Wiley-VCH,19

The principal idea of this volume is to offer a Capita Selecta of unconventional and thought-provoking topics in organometallic chemistry, presented by experts in each field. As intended, this approach leads either to reviews covering a specific uncommon class of organometallic compounds or to overviews which relate uncommon physical properties with various classes of organometallic compounds. The contributions are streamlined thus onto two main axes - unusual properties reflecting structures and bonding situations, on the one hand, and uncommon structural features or structure-reactivity relationships, on the other. Extensive cross-referencing of useful information is provided, making this volume accessible for people working in rather different areas of organometallic chemistry.

The synthesis of molecules with 'extreme' properties is a challenge for all those working in organometallic chemistry, irrelevant of theoretical/computational, synthetic or application interests. This book presents case studies at the interface of these overlapping interests.

Unusual Structures and Physical Properties in Organometallic Chemistry:

• Provides test cases for computational and theoretical models
• Presents a challenge for synthetic chemists
• Provides ideal show cases for analytical techniques

This volume will be an invaluable reference for researchers in organometallic chemistry, computational and theoretical chemistry, NMR and other spectroscopic methods.

What do a pharmaceutical, polymer and solid state chemist have in common? Organometallic chemistry of course, since progress in their diverse fields has at many times relied on this. It is a discipline which stands at the crossroads of so many branches of chemistry, with industrial applications ranging from the gram to megatonne scale. This book aims to introduce undergraduates to the utility of organotransition metal chemistry, a discipline of importance to scientists and technologists in a variety of industry sectors. The main focus will be on the reactivity of organometallic compounds of the transition metals, supported by discussion of structure and bonding and their implications. The aim, on completion of the course, is that a student will be equipped to recognize the key classes of organometallic compounds, their methods of characterization, possible synthetic routes and anticipated reactivity. Ideal for the needs of undergraduate chemistry students, Tutorial Chemistry Texts is a major series consisting of short, single topic or modular texts concentrating on the fundamental areas of chemistry taught in undergraduate science courses. Each book provides a concise account of the basic principles underlying a given subject, embodying an independent-learning philosophy and including worked examples.

Over the past 20 years aqueous organometallic catalysis has found applications in small- scale organic synthesis in the laboratory, as well as in the industrial production of chemicals with a combined output close to one million tons per year. Aqueous/organic two-phase reactions allow easy product-catalyst separation and full catalyst recovery which mean clear benefits not only in economic but also in environmental and green chemistry contexts. Instead of putting together a series of expert reviews of specialized fields, this book attempts to give a comprehensive yet comprehensible description of the various catalytic transformations in aqueous systems as seen by an author who has been working on aqueous organometallic catalysis since its origin. Emphasis is put on the discussion of differences between related non-aqueous and aqueous processes due to the presence of water. The book will be of interest to experts and students working in catalysis, inorganic chemistry or organic synthesis, and may serve as a basis for advanced courses.

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.

In view of increasing interest in organofluorine compounds, this book was undertaken to describe biological and physical properties of organofluorine compounds, synthetic methods of these, their roles in pharmaceutical, agrochemical and material sciences. In particular, the book will emphasize on the usefulness of fluorination reaction, availability of fluorination agents, so that even graduate students who are unfamiliar to this field can understand and participate in this fascinating heteroatom chemistry.

Embarking on a new millennium, the book in hands describes the recent developments of organsoselenium chemistry in all facets. Various distinguished scientists have contributed, with their skill and expertise, making this book a valuable source for synthetic oriented organic chemists and for those, who want to get a first insight into the chemistry of selenium.

Biological inorganic chemistry is a field of research at the interface of inorganic and biological chemistry. The rapidly developing insights into the role of metals in biological systems has far-reaching implications not only for biological science but also for related disciplines, ranging from molecular medicine to the environment. In each volume the reader, whether engaged in chemistry, biochemistry, biology or molecular medicine, receives a comprehensive summary and critical overview of a topic of high current interest written by leading international experts.

This edited work contains eight extensive, review-type contributions by leading scientists in the field of synthetic metals. The authors were invited by the organisers of the International Conference on Science and Technology of Synthetic Metals '98 (ICSM'98) to review the progress of research in the past two decades in a unifying and pedagogical manner. The present work highlights the state-of-the-art of the field and assesses the prospects for future research.

General The making and breaking of carbon-metal bonds is fundamental to all the p- cesses of organometallic chemistry and moreover plays a significant role in - mogeneous as well as heterogeneous catalysis. This rather blunt statement - phasises the extent to which a proper understanding of the structure, energetics and reactivity of C-M bonds is at the core of the discipline. In order to accept it, a proper definition of the terms involved is required. Quite simply we define the metal-carbon bond in its broadest sense to embrace carbon linked to transiti- metals, lanthanides and actinides, and main group metals. We do not dist- guish between formally covalent single or multiple bonding on the one hand and q-bonding on the other. In the studies to be described in the following chapters, the emphasis will be on transition metal complexes and insofar as the fun- mentals come under scrutiny, simple metal alkyls or related species (metal al- nyl, alkynyl, aryl, or allyl) will play an emphatic part. The central role of metal alkyls and their congeners and especially the role of their metal carbon linkage in homogeneous catalysis may be appreciated by considering some key reaction steps leading to their formation or breakdown. There follows a few prominent examples of transition metal mediated stoichiometric or catalytic processes: - In homogeneous hydrogenation of double bonds, the stepwise reaction of an q2-coordinated alkene with dihydrogen gives first an alkyl metal hydride, and then the decoordinated alkane by elimination.

While the lanthanides (strictly defined as the 14 elements following lanthanum in the periodic table, but as normally used also include lanthanum itself) have several unique characteristics compared to other elements, their appearance in the history of the development of organometallic chemistry is rather recent. Since the f orbitals are filled gradually from lanthanum ( Xe]4f ) to lutetium ( Xe]4fl4), they are regarded as the f-block elements, which are discriminated from the d-block transition elements. This book was edited as the second volume of "Topics in Organometallic Chemistry," aiming at an overview of recent advances of chemistry and organic synthesis of lanthanides. Since scandium (Sc) and yttrium (Y) (which lie above the lanthanides and have similar characteristics) are also included, this book covers rare earth chemistry. Recently, especially in this decade, the chemistry and organic synthesis of lanthanides have developed rapidly as one of the most exciting areas. An international team of authors has been brought together in order to provide a timely and concise review of current research efforts such as lanthanide catalysis in small molecule organic synthesis especially focused on carbon-carbon bond-forming reactions, chemistry and organic synthesis using low-valent lanthanides such as diiodosamarium, asymmetric catalysis, lant- nide-catalyzed polymer synthesis, and polymer-supported lanthanide catalysts used in organic synthesis. Principles of organolanthanide chemistry are sum- rized in the first chapter. I am sincerely grateful to Drs. R. Anwander, E. C. D- dy, H. Gr6ger, Z. Hou, H. Kagan, G. Molander, J. L. Namy, M. Shibasaki, Y.

This book is devoted to the interaction between elemental metals and (in)organic ligands in different reaction conditions. Metals could be activated for further reactions as cryosynthesis, electrosynthesis and tribosynthesis, some of them with or without ultrasonic and microwave treatment. The kinetics of metal dissolution in various non-aqueous media is discussed in detail.

Many methods are used nowadays to synthesize coordination compounds. Metal complexes are obtained mainly by the direct interaction of the components (the ligands and a source of the complex-forming metal), as a result of ligand and metal exchange, and under the conditions of template synthesis, which also include the method of nascent reagents. In these methods the source of the metal is either its salts or carbonyls. At the same time, it has long been known that coordination compounds may be obtained as a result of direct synthesis from zero-valent metals. Methods for the synthesis of complex compounds under the conditions of gas-phase reactions, oxidative dissolution of zero-valent metals in non-aqueous media, and in the solid phase have been developed. These methods have become the basis of a new field in synthetic chemistry - the direct synthesis of coordination and organometallic compounds from zero-valent metals.

Particular aspects of the above problem have been described in a series of reviews and monographs. However, on the whole these main parts of the direct synthesis of metal complexes has not been dealt with in the review and monograph publications on coordination chemistry. So, the main objective of this book is to analyze, discuss and generalize the existing information in the area of direct reactions leading to the coordination and organometallic reactions.

Some methods of direct synthesis have been developed in the former USSR (in particular, a lot of works on cryosynthesis, pioneered (1972-1973) and recent works on electrosynthesis) but, in spite of their novelty and/or wide applicability, they are practically unknown elsewhere due to the language barrier. Thus, another objective of this book is to acquaint the readers with the mentioned achievements.

Every chapter contains the tables which describe all the reported data on direct reaction between metal atoms, metal particles or bulk metals with (in)organic ligans. There are some illustrations also (for example, the scheme of the reactor for gas-phase reaction between metal small particles and &bgr;-diketones).

This text provides an invaluable introduction for all undergraduate students of chemistry and a useful reference of more advanced students. The main group elements (including silicon and phosphorus, but not Group VI) and the transition elements are discussed. Emphasis is laid on structure, bonding, preparation and general reactions, with many specific examples of the uses of organometallics in organic synthesis interspersed throughout the text.

Stability constants are fundamental to understanding the behavior of metal ions in aqueous solution. Such understanding is important in a wide variety of areas, such as metal ions in biology, biomedical applications, metal ions in the environment, extraction metallurgy, food chemistry, and metal ions in many industrial processes. In spite of this importance, it appears that many inorganic chemists have lost an appreciation for the importance of stability constants, and the thermodynamic aspects of complex formation, with attention focused over the last thirty years on newer areas, such as organometallic chemistry. This book is an attempt to show the richness of chemistry that can be revealed by stability constants, when measured as part of an overall strategy aimed at understanding the complexing properties of a particular ligand or metal ion. Thus, for example, there are numerous crystal structures of the Li+ ion with crown ethers. What do these indicate to us about the chemistry of Li+ with crown ethers? In fact, most of these crystal structures are in a sense misleading, in that the Li+ ion forms no complexes, or at best very weak complexes, with familiar crown ethers such as l2-crown-4, in any known solvent. Thus, without the stability constants, our understanding of the chemistry of a metal ion with any particular ligand must be regarded as incomplete. In this book we attempt to show how stability constants can reveal factors in ligand design which could not readily be deduced from any other physical technique.

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.

The analogy between the chemistry of molecular transition metal clusters and the processes of chemisorption and catalysis at metal surfaces (the Cluster Surface analogy) has for a number of years provided an interplay between experimental and theoretical inorganic and physical chemists. This collaborative approach has borne fruit in the use of well-defined modes of metal-ligand bonding in discrete molecular clusters, models for metal-ligand binding on surfaces. Some of the key topics discussed in this book are: mechanisms of the fluxional behaviour in clusters in the liquid phase and the connections with diffusion processes on extended surfaces, and the role of metal-metal bond breaking in diffusion; analogies in the structure of chemisorbed species and related ligands on metallic clusters; analogies between benzene surface chemistry on extended metal surfaces and on metal surfaces in molecular cluster compounds with particular reference to structural distortions; and the role of mobile precursors for dissociation of chemisorption on extended metals and on clusters.

In the last 15 years aqueous organometallic chemistry and catalysis has emerged from being a laboratory curiosity to become an established field of research. Topics reviewed here include mechanistic studies on the effect of water on catalyzed reactions, the preparation of water soluble phosphines as ligands for catalysis, metal catalyzed organic reactions in water (hydrogenation, hydroformylation, carbonylation, olefin metathesis, hydrophosphination, etc.), chiral ligands and enantioselective catalysis, organometallic radical photochemistry in aqueous solutions, bioorganometallic chemistry, organometallic reactions of biopolymers, and catalytic modification of biomembranes. The summary of recent results is supplemented by an assessment of probable future research trends. Audience: Researchers in both academia and industry, as well as graduate students of homogeneous catalysis.