This book presents an advanced state-of-the-art report on the Fischer and Schrock type carbyne complexes and demonstrates their wide application to organic and organometallic synthesis, as well as their considerable role in metathesis. Most of the articles are written by leading researchers in this field, describing their fascinating research in their own words. This carbyne book discusses in detail the breadth and diversity of metal-carbon multiple bond chemistry of different d and f-block elements. Besides theoretical, structural, photochemical and electrochemical studies, this volume provides a fascinating introduction to heterometallic carbon-bridged compounds to conjugated complexes and polymers derived from metal-carbyne building blocks. An extensive part of this book discusses aspects of olefin metathesis, metal-induced addition, cycloaddition and carbon-carbon coupling reactions by well-characterized carbene and carbyne complexes. (abstract) This book presents an advanced state-of-the-art report on the Fischer and Schrock type carbyne complexes, discussing specific aspects of the metal carbon multiple bond chemistry of different d and f-block elements, such as synthetic, theoretical, structural, photochemical and electrochemical studies. Special chapters focus on catalysis and olefin metathesis as well as metal induced addition, cycloaddition and carbon-carbon coupling reactions.

Why has the energetics of organometallic species become an area of recognized importance? What methods are available to obtain information on reaction enthalpies and bond "strengths"? What other methods are likely to be used in the future? Is the present thermochemical data bank satisfactory for our needs? How accurately can we estimate the energetics of organometallic reactions? Can theory offer reliable help? Which are the main problems to be tackled by the experimentalist? These are some of the questions addressed in this text, which contains contributions by many of the leading groups in the are or organometallic thermochemistry.

This volume dedicated to the memory of Marcel Sergent who was a leader in this field for many years, addresses past achievements and recent developments in this vibrant area of research. Large classes of ligated transition metal clusters are produced either exclusively or most reliably by means of high-temperature solid-state reactions. Among them, the Chevrel-Sergent phases and related materials have generated enormous interest since their discovery in 1971. Today, these materials and their numerous derivatives still constitute a vivid area of research finding some applications not only in superconductivity, but also in catalysis, optics or thermoelectricity to mention a few.

The past 15 years have seen tremendous progress in manganese chemistry, with the low cost of this metal making it an attractive choice as a functional group in organic syntheses. Surveying key compounds and reaction intermediates used in organic syntheses, this is the first volume in the Patai Series to focus on manganese in organic and organometallic chemistry. With contributions by leading experts, the book delivers the usual high quality of the Patai series. It also emphasizes novel applications in organic synthesis as well as technological trends in industrial, biomedical, and materials science.

Preparative Polar Organometallic Chemistry is a collection of laboratory procedures for the synthesis and functionalization of organoalkali and Grignard compounds. The second volume with methods for generation and transformation of compounds bearing the metal at an sp3 carbon complements the first in which the metal was bound to an sp2 carbon atom in the reagent. Synthetically important intermediates such as metallated S, S-acetales, imines, nitriles, isonitriles and ketones are illustrated. All procedures have been worked out in full detail and tested in the author's own laboratory. Both books are intended to be practical bench-top laboratory manuals for working organic chemists, from the student to the advanced scientist.

Organometallic chemistry belongs to the most rapidly developing area of chemistry today. This is due to the fact that research dealing with the structure of compounds and chemical bonding has been greatly intensified in recent years. Additionally, organometallic compounds have been widely utilized in catalysis, organic synthesis, electronics, etc. This book is based on my lectures concerning basic organometallic chemistry for fourth and fifth year chemistry students and on my lectures concerning advanced organometallic chemistry and homogeneous catalysis for Ph.D. graduate students. Many recent developments in the area of organometallic chemistry as weIl as homogeneous catalysis are presented. Essential research results dealing with a given class of organometallic compounds are discussed briefly. Results of physicochemical research methods of various organometallic compounds as weIl as their synthesis, properties, structures, reactivities, and applications are discussed more thoroughly. The selection of tabulated data is arbitrary because, often, it has been impossible to avoid omissions. Nevertheless, these data can be very helpful in understanding properties of organometaIlic compounds and their reactivities. All physical data are given in SI units; the interatomic distances are given in pm units in figures and tables. I am indebted to Professor S. A. Duraj for translating and editing this book. His remarks, discussions, and suggestions are greatly appreciated. I also express gratitude to Virginia E. Duraj for editing and proofreading.

There are only few topics in organometallic chemistry, which have stimulated research activities in as many areas, as transition-metal carbene (alkylidene) complexes. About 25 years after the first planned synthesis of a carbene complex in E.O. Fischer's laboratory in Munich the NATO Advanced Research Workshop on Transition-Metal Carbene Complexes was the first meeting which, brought together scientists from different disciplines to discuss inorganic, organic, theoretical structural catalysis-related aspects of metal carbene chemistry. The 70th birthday of Professor E.O. Fischer was a good occasion for this enterprise. The organizers of the meeting (K.D. Dotz, Marburg; F.R. KreiBl, Munchen; U. Schubert, Wurzburg) were encouraged by the fact that most of the leading scientists in this area were able to participate in the workshop. The very high standard of the contributions is reflected in this book, which contains papers from the majority of the participants. The Proceedings show the state of the art in metal carbene chemistry and will hopefully be a landmark in the development of this area of chemistry. Generous financial support for the workshop and for the preparation of this book was provided by the Scientific Affairs Division of NATO and some companies. The organizers also acknowledge the efforts of the staff of the Bildungs zentrum der Hans-Seidel-Stiftung in Wild bad Kreuth for creating a pleasant and stimulating atmosphere during the conference."

Surface organometallic chemistry is a new field bringing together researchers from organometallic, inorganic, and surface chemistry and catalysis. Topics ranging from reaction mechanisms to catalyst preparation are considered from a molecular basis, according to which the "active site" on a catalyst surface has a supra-molecular character. This. the first book on the subject, is the outcome of a NATO Workshop held in Le Rouret. France, in May. 1986. It is our hope that the following chapters and the concluding summary of recommendations for research may help to provide a definition of surface organometallic chemistry. Besides catalysis. the central theme of the Workshop, four main topics are considered: 1) Reactions of organometallics with surfaces of metal oxides, metals. and zeolites; 2) Molecular models of surfaces, metal oxides, and metals; 3) Molecular approaches to the mechanisms of surface reactions; 4) Synthesis and modification of zeolites and related microporous solids. Most surface organometallic chemistry has been carried out on amorphous high-surf ace-area metal oxides such as silica. alumina. magnesia, and titania. The first chapter. contributed by KNOZINGER. gives a short summary of the structure and reactivity of metal oxide surfaces. Most of our understanding of these surfaces is based on acid base and redox chemistry; this chemistry has developed from X-ray and spectroscopic data, and much has been inferred from the structures and reactivities of adsorbed organic probe molecules. There are major opportunities for extending this understanding by use of well-defined (single crystal) oxide surfaces and organometallic probe molecules."

This lecture note gives an analysis of electronic structure effects for a new class of molecular solids, i. e. one-dimensional organometal lic systems formed by transition-met. l atoms that are embedded in a matrix of macrocyclic organic ligands. These systems as well as orga nic metals have focused considerable interest due to the potential formation of high-mobility charge carriers. For the present author it is difficult to participate in this restriction on a single physical property (i. e. high electronic conductivities, technical applications, etc. ). The lecture note is hopefully a small contribution to enhance the general understanding of certain electronic properties in organo metallic polymers. Those problems have been considered in the first place that seem to form a theoretical deficit in one specific field of solid-state chemistry. For the reader it will become evident that this contribution is a compromise always guided and limited by boundaries: i) An attempt to present problems to a .chemical. audience which have their roots in solid-state physics. ii) The model calculations are limited by the currently available computational facilities. This .boundary. implies that the compu tational data a e subject to severe theoretical approximations. iii) Theorists have often a strong tendency to identify their numeri cal results and models with physical effects. Also this lecture note is not free of this almost universal trend. Nevertheless the author hopes that this text leads to some insight into a rather modern research field. M. e. B6hm I."

Polar organometallic compounds are indispensable for the synthetic chemist. As this book shows, these almost ideal reagents are easy to prepare with high specificity under mild conditions and yet react quite readily with a great variety of substrates. Many compounds can be metallated directly at positions which would otherwise be difficult to substitute. Functional groups and heteroatoms already present in a molecule direct metallation to sites in their vicinity. The rules which govern polar organometallic chemistry often are not dominated by the usual n-delocalization and inductive effects; dipolar interactions, chelation, polarization, etc. often can be much more important. This affords novel synthetic opportunities. A good example is the development of a basically new type of aromatic substitution chemistry not based on positively charged intermediates. Seebach's injunction, "Thinking of polar organometallic compounds as carbanions is an impoverishment rather than a simplification" (International Symposium, Chemistry of Carbanions, Durham 1984), stresses the need to consider the metal not only as an integral, but perhaps also as the key component of these reagents. Rather than wandering off as solvated cations and acting as uninvolved spectators, the metals, rather than the anion moieties, can initiate and govern the subsequent reactions. To the founders of this field, e. g. Grignard, Ziegler, Gilman, Wittig, and their followers, the metal was critical. The title of Schlosser's book, "Polare Organometalle," certainly was apt.

The present volume Uranium C5 covers the physical properties of U0 - the production 2 and preparation of U0 were already treated in Uranium C4, whereas the chemical proper 2 ties will be the subject of the forthcoming part C6. U0 is the most important chemical compound in all aspects of nuclear technology. 2 It is and will be for the foreseeable future the fuel for all light and heavy water reactors as well as (in the mixed crystal with Pu0 ) for the fast breeder reactors. Therefore, the 2 nuclear engineer has to understand the behavior of U0 under all conditions existing during 2 operational (and possibly failure) states of a nuclear reactor, e. g. , not only in the solid state but also to some extent in the liquid and gaseous states. Besides high scientific interest in the sometimes unique or unusual properties, e. g. , at low temperatures, a lot of data and physical properties which are critical for its use as a nuclear fuel have been determined more or less accurately. Creep, swelling, irradiation densification, and fission gas behavior in the fuel are properties which have been evaluated up to the high temperatu res (near the melting point) which may exist in U0 fuel due to its low thermal conductivity. 2 Besides these more technical data there have been accumulated a lot of important physical data, e. g.

The past decade has seen a dramatic acceleration of activity and interest in phenomena surrounding lanthanide and actinide organo metallic compounds. Around the world, active research in organo-f element synthesis, chemistry, catalysis, crystallography, and quantum chemistry is in progress. This activity has spanned a remarkably wide range of disciplines, from synthetic/mechanistic inorganic and organic chemistry to radiochemistry, catalytic chemistry, spectroscopy (vibra tional, optical, magnetic resonance, photoelectron, Mossbauer), X-ray and neutron diffraction structural analysis, as well as to crystal field and molecular orbital theoretical studies at the interface of chemistry and physics. These investigations have been motivated both by fundamental and applied goals. The evidence that f-element organo metallic compounds have unique chemical and physical properties which cannot be duplicated by organometallic compounds of d-block elements has suggested many new areas of endeavor and application. For these reasons, a great many scientists felt the need for some international forum devoted exclusively to the subject of lanthanide and actinide organometallic compounds. In September of 1978, a NATO Advanced Study Institute entitled, "Organometallics of the f-Elements," was held at the SOGESTA Conference Center near Urbino, Italy. It was the universal feeling of the partic ipants that this first meeting was a great success and that vital international communication and collaboration had been stimulated. The principal lectures at this Institute were published by Reidel in 1979 as part of the NATO ASI Monograph Series ("Organometallics of the f-Elements," T. J. Marks and R. D. Fischer, editors)."

Soluble catalysts are used extensively in many branches of chemistry and are indeed a vital constituent of many natural processes. They find wide application throughout the chemical industry where they assist in the production of several million tonnes of chemicals each year. Since homogeneous systems, especially those incorporating transition metals, often function effectively under milder conditions than their heterogeneous counterparts, they are becoming increasingly important at a time when the chemical industry in particular, and society in general, is seeking ways of conserving energy and of making the best possible use of available resources. My principal objective in. writing this book is to engender sufficient enthusiasm for, and knowledge of, the subject in the reader that he or she will be encouraged to begin, or continue, to make their own contribution to advancing our knowledge of homogeneous catalysis. After attempting to acquaint the reader with some of the ground rules I have tried to describe the .present scope, and the future potential, of this fascinating field of chemistry by drawing both on academic and on industrial data sources. This approach stems from a personal conviction that future progress could be considerably hastened by a more meaningful dialogue between chemists working both in industrial and in academic research institutions. Wherever possible, examples of the commercial application of homogeneous catalyst systems have been included and no attempt has been made in any way to disguise the many unresolved questions and exciting challenges which still pervade this rapidly developing area."

The second edition of Organometallic Compounds (1960) was used not only by specialists but also as an undergraduate textbook. The third edition, recently published in two volumes, is about three times the length of the second and contains considerably more factual material than is appropriate for a student textbook. Therefore we believe that a shorter treatment would be welcome. In planning this book the authors have emphasized matters more of prin ciple than of detail, and have included in the first two chapters some general discussion of the properties and syntheses of organometallic compounds that is not to be found in the larger work. Some aspects of the organic chemistry of arsenic, and of silicon with particular reference to silicone polymers, are also included. Most university teachers of chemistry are becoming seriously concerned about the relentless increase in the amount and complexity of the material that is squeezed into undergraduate chemistry courses. With this in mind the authors have tried to cut detail to a minimum, but readers will find that the relative amount presented varies considerably between the various topics discussed. In general the treatment is more extensive than usual only if either or both of these conditions are met: (1), the subject has significant bearing on other major branches of chemistry including im portant industrial processes; (2), the topic is commonly misunderstood or found to be confusing."

The aim of this Compilation has been to provide a comprehensive, non critical source of information concerning organometallic compounds. The scope is limited to the compounds containing at least one carbon-metal bond. The information includes methods of preparation, properties, chemical reactions and applications. The First Edition comprised the literature from 1937 to 1958. The Second Edition is completely revised and extended through 1964. The literature prior to 1937 was thoroughly covered by E. Krause and A. von Grosse in 11 11 Die Chemie der metall-organischen Verbindungen, Verlag von Gebrueder Borntraeger, Berlin, 1937. Our work consists of three volumes. Volume I contains derivatives of the transition metals of Groups III through VIII of the Periodic Table. Volume II contains derivatives of germanium, tin and lead. Volume Ill contains derivatives of arsenic, antimony and bismuth. The Compilation is based on searches through Chemical Abstracts. The collection of references for 1964 was completed before the Subject Indexes to Volumes 60 and 61 of the Abstracts were available; thus some omissions in the coverage of that year are possible. We have attempted to make the coverage of the literature complete in order that the Compilation may have best utility to the chemist, chemical engineer, patent attorney and editor. In the interest of brevity, certain numerical data are omitted, but references to the original literature are given. Yield data are rounded to two significant figures. Wherever possible, tables have been used. The entries in the Bibliography section include references to Chemical Abstracts.

___ -"S, . . C"'O, . . . P""E This non-critical compilation of literature data on organic drivatives of arsenic, antimony, and bismuth, reported after 1936, was prepared to provide an easy reference to the methods of their synthesis and to their physical and chemical properties. Biological properties of the organic derivatives of these three elements were not considered. The presence volume is based upon Chemical Abstracts (CA), Volume 31 (1937) through Volume 53(1959), and upon "Current Chemical Papers," published by the Chemical Society (London), issues for January through June 1960. For references published prior to 1937 the reader is referred to "Die Chemie der metall-organischen Verbindugen/' by E. Krause and A. vor. Grosse, Verlag von Gebrlider Borntraeger, Berlin, 1937. It should be pointed out that only compounds containing at least one carbon arsenic, carbon-antimony, and carbon-bismuth bond, respectively, are included in the survey. HIGHLIGHTS The discovery of the chemotherapeutic efficacy of monosodium- arsanilate, 3,3'-diamino-4,4' -dihydroxyarsenobenzene, and 3-amino-4,4'-dihydroxy-3' (sulfinomethylamino)arsenobenzene sodium salt (Atoxyl, Salvarsan, and Neosalvarson, respectively) provided inpetus to extensive research of organoarsenicals, which slakened only after the discovery of antibiotics. After 1936, a great variety of substituted arenearsonic and diarylarsinic acids was prepared and reduced to various types of trivalent arsenic derivatives, Further modifications of the Bart method were made, and aryldiazonium fluoroborates, chlorozincates, and chloroferrates, which are more stable than aryldiazonium chlorides, were introduced as the arylat ing agents in the preparation of aromatic derivatives of arsenic."

Modern organic synthesis has paid much attention to the chemistry of small carbocycles. Vinylidenecyclopropanes (VDCPs), which have strained cyclopropyl group connected with an allene moiety and yet are thermally stable and reactive substances in organic chemistry, are versatile intermediates in organic synthesis. In this volume, Dr. Lixiong Shao, Dr. Jianmei Lu and Prof. Dr. Min Shi review their investigations on the chemistry of VDCPs, mainly including the preparation, the reactivities upon treatment with Lewis or Bronsted acid, as well as transition metal catalysts and some other miscellaneous analogues. The contributions aroused a renaissance of cationic intermediates in the chemistry of VDCPs.

Chromic acid and chromium oxide are the two versatile Cr(VI) oxidants known to organic chemists for decades. The introduction of the Core's reagent , viz: pyridinium chlorochromate, in 1975 followed by the publications on several Cr(VI) oxidizing agents containing the -onium chromates and halochromates in the last three decades have very much changed the chemistry of oxidations with Chromium VI. Several of these new reagents have been shown to be mild so that they can be handled easily and the reacton products may also be controlled. Some of them are highly selective oxidants for positions like allylic hydroxylic group, etc., and some other are highly regioselective. The information on more than 36 such reagents reported in various internationally reputed journals spanning about 280 references have been collected and provided in this book in such a manner that it will be very useful for professionals, researchers, teachers and graduate students working in organic synthesis.

The first authoritative book on using silver cations in organic chemistry--for catalysis and more

With more sophisticated catalytic methodologies fueling a resurgence in the study of cation-based chemistry, gold and platinum have stepped to the fore as the unique agents used to create new chemical reactions. Although these metals have become a primary focus of researchers in the field, another coinage metal that is often overlooked--but is as powerful as the others--is silver, a far less costly alternative to gold and platinum in aiding the development of new reactions.

Making a strong case for the use of silver as a catalyst and structural element in organometal constructs, this authoritative book is the first to explore the benefits of using silver in organic chemistry by taking a close look at silver's unique reactivity and structural characteristics for the development of new methods and materials. "Silver in Organic Chemistry" is: The first book to address catalysis using silver, whose use in organic chemistry is on the verge of explodingA resource for researchers wishing to do chemistry with silver cations, an area that stands in the shadow of gold chemistry, but still glistens, demonstrating that all that glitters is not gold--sometimes it's silver A guide for "first attempts" in working with silver cationsEdited by a very well-respected, highly visible authority in this field

"Silver in Organic Chemistry" promotes further scientific discussion by offering important new ways to examine the future possibilities of an emerging field. By elevating the importance of silver chemistry, this thought-provoking guide illustrates how this versatile metal can become an increasingly significant player in opening the door to new catalytic organic reactions and new organometal materials.

Focusing on preparation and applications in synthesis and catalysis, this book finally closes a gap in the literature by summarizing this hot topic for the first time.

As such, it gathers in one volume the key features of metal vinylidene and allenylidene complexes as well as reactive species and covers applications in metathesis, polymerization, molecular materials, carbon rich compounds and fine chemical production. The emphasis here is on the selective transformations of alkynes and enynes plus simple and complex molecules containing a triple C-C bond.

The result is a must-have ready reference for organic, catalytic, complex, theoretical and polymer chemists, as well as those working with/on organometallics.

This completely revised and updated second edition of Organometallic Compounds in the Environment treats environmental organometallic chemistry as an integrated and coherent subject area in its own right, bringing together contributions from leading scientists throughout the world.

The Introduction summarizes and explores those properties of organometallic compounds that are relevant to their behaviour and impact in the natural environment. Subsequent chapters cover those elements whose organometallic derivatives are especially important in the environmental context. The natural formation of organometallics from inorganic precursors under environmental conditions is also treated in detail. An important underlying theme running through the work is the biological properties and toxicities of the organometallic species present in the environment. In general a full speciation approach is taken, where the full molecular identities of the compounds concerned are considered.

Research workers in the fields of organometallic compounds and their environmental impact, as well as those interested in organometallic and environmental chemistry generally, will welcome this new edition. It will also be invaluable as a source book to lecturers teaching courses at undergraduate or graduate level in applied, analytical, industrial, organometallic or environmental chemistry, or in environmental science in general.

This book examines the occurrence, toxicity, analysis and typical concentrations of organometallic compounds in various environmental samples. These include aqueous and effluent, crop and plant, soil and sediments, atmospheric and living organisms in a detailed and systematic manner. A knowledge of the chemical structure and concentration of organometallic compounds throughout the ecosystem is important in working out the pathways and mechanisms by which metals distribute themselves throughout the environment. The principal elements discussed are mercury, lead, tin and arsenic. Other organometallic compounds, including cadmium, antimony, selenium, germanium, manganese, copper and nickel, which occur in the environment less frequently and at lower concentrations are also discussed. Contents

1. Introduction
2. Concentrations of Organometallic Compounds in the Ecosystems
3. Toxic Effects of Organometallic Compounds
4. Toxicity Testing
5. Bioaccumulation Processes
6. Analysis of Organometallic Compounds in the Environment

Occurrence and Analysis of Organometallic Compounds in the Environment is essential reading for all organometallic and analytical chemists, environmentalists, and toxicologists working in the field.