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.

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.

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.

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.

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.

Advances in Organometallic Chemistry, Volume 74, the latest release in this longstanding serial, is known for its comprehensive coverage of topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more. It is ideal for a wide range of researchers involved in organometallic chemistry, with this updated release including chapters on Metal dendrimers used in biomedical applications, Sigma-bond activation reactions induced by unsaturated osmium (IV) complexes with bulky phosphines, Base metal pincer complexes, and more.

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.

E.O. Fischer received the Nobel prize in 1973 for the investigations of complexes with a formal metal atom-carbon double bond. Among these, the Iron-Carbene species is readily available and has proved to be a versatile reagent in organic syntheses. It is rather simple to tune the electronicproperties of this Fischer Carbene and to control reactivity and stereospecificity of the reagent in, e.g., cyclopropanation reactions. This first volume of the "Scripts in Inorganic and Organome- tallic Chemistry" addresses graduate students in the fields ofcoordination compounds and organic synthesis. It covers the chemistry and structural aspects of iron-carbon com- pounds with a iron-carbon double bond. The first part deals with the carbene moiety, the second with vinylidene ligands.

Early Main Group Metal Catalysis gives a comprehensive overview of catalytic reactions in the presence of group 1 and group 2 metals. Chapters are ordered to reaction type, contain educational elements and deal with concepts illustrated by examples that cover the main developments. After a short introduction on polar organometallic chemistry and synthesis of early main group metal complexes, a variety of catalytic reactions are described, e.g. polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, as well as enantioselective and Lewis-acid catalysis. The book addresses organic chemists and researchers in industry interested in the state-of-the-art and new possibilities of early main group metal catalysis as well as newcomers to the field. Written by a team of leaders in the field, it is a very welcome addition to the area of main group metal chemistry, and to the field of catalysis.

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.

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.

This book systematically describes the design and synthesis of MOF-related materials and the electrochemical energy storage-related research in the field of batteries. It starts with an introduction to the synthesis of MOF-based materials and various MOF derivatives, such as MOF-derived porous carbon and MOF-derived metal nanoparticles. This is followed by highlighting the interesting examples for electrochemical applications, illustrating recent advances in battery, supercapacitor, and water splitting. This book is interesting and useful to a wide readership in the various fields of chemical science, materials science, and engineering.

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."

Knowledge on endohedral metallofullerenes (EMFs) has increased dramatically during the last decade. Numerous research findings have been reported, making it an opportune time to provide a systematic update on EMFs. Endohedral Metallofullerenes: Basics and Applications presents the most comprehensive review on all aspects of EMFs including their generation, extraction and isolation, structural issues, theories, intrinsic properties, chemical behaviors, and potential applications. In this book, the editors have collected an impressive amount of information regarding this family of a truly sui generis form of matter. The book's authors were chosen for their specific expertise in EMF research and have been gathered from top research groups from around the world. Graduate students, newcomers to the field, and experienced researchers alike will find this book a highly useful reference on the topic.

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."

The handbook comprehensively covers the field of inorganic photochemistry from the fundamentals to the main applications. The first section of the book describes the historical development of inorganic photochemistry, along with the fundamentals related to this multidisciplinary scientific field. The main experimental techniques employed in state-of-art studies are described in detail in the second section followed by a third section including theoretical investigations in the field. In the next three sections, the photophysical and photochemical properties of coordination compounds, supramolecular systems and inorganic semiconductors are summarized by experts on these materials. Finally, the application of photoactive inorganic compounds in key sectors of our society is highlighted. The sections cover applications in bioimaging and sensing, drug delivery and cancer therapy, solar energy conversion to electricity and fuels, organic synthesis, environmental remediation and optoelectronics among others. The chapters provide a concise overview of the main achievements in the recent years and highlight the challenges for future research. This handbook offers a unique compilation for practitioners of inorganic photochemistry in both industry and academia.

The Organometallic Chemistry of N-heterocyclic Carbenes describes various aspects of N-heterocyclic Carbenes (NHCs) and their transition metal complexes at an entry level suitable for advanced undergraduate students and above. The book starts with a historical overview on the quest for carbenes and their complexes. Subsequently, unique properties, reactivities and nomenclature of the four classical NHCs derived from imidazoline, imidazole, benzimidazole and 1,2,4-triazole are elaborated. General and historically relevant synthetic aspects for NHCs, their precursors and complexes are then explained. The book continues with coverage on the preparation and characteristics of selected NHC complexes containing the most common metals in this area, i.e. Ni, Pd, Pt, Ag, Cu, Au, Ru, Rh and Ir. The book concludes with an overview and outlook on the development of various non-classical NHCs beyond the four classical types. Topics covered include: * Stabilization, dimerization and decomposition of NHCs * Stereoelectronic properties of NHCs and their evaluation * Diversity of NHCs * Isomers of NHC complexes and their identification * NMR spectroscopic signatures of NHC complexes * normal, abnormal and mesoionic NHCs The Organometallic Chemistry of N-heterocyclic Carbenes is an essential resource for all students and researchers interested in this increasingly important and popular field of research.

The first and ultimate guide for anyone working in transition organometallic chemistry and related fields, providing the background and practical guidance on how to efficiently work with routine research problems in NMR. The book adopts a problem-solving approach with many examples taken from recent literature to show readers how to interpret the data. Perfect for PhD students, postdocs and other newcomers in organometallic and inorganic chemistry, as well as for organic chemists involved in transition metal catalysis.

This updated, second edition retains its classroom-tested treatment of physical chemistry of metallurgical topics, such as roasting of sulfide minerals, matte smelting, converting, structure, properties and theories of slag, reduction of oxides and reduction smelting, interfacial phenomena, steelmaking, secondary steelmaking, role of halides in extraction of metals, refining, hydrometallurgy and electrometallurgy, and adds new data in worked-out examples as well as up-to-date references to the literature. The book further explains the physical chemistry of various metallurgical topics, steps involved in extraction of metals, such as roasting, matte smelting/converting, reduction smelting, steelmaking reactions, deoxidation, stainless steelmaking, vacuum degassing, refining, leaching, chemical precipitation, ion exchange, solvent extraction, cementation, gaseous reduction and electrowinning. Each topic is illustrated with appropriate examples of applications of the technique in extraction of some common, reactive, rare, or refractory metal together with worked out problems explaining the principle of the operation. The problems require imagination and critical analyses and also encourage readers for creative application of thermodynamic data in metal extraction. Updates and condenses text throughout the book by sequential arrangement of paragraphs in different chapters; Maximizes readers' understanding of the physicochemical principles involved in extraction/production of common and rare/reactive metals by pyro- as well as hydrometallurgical routes; Reinforces concepts presented with worked examples in each chapter explaining the process steps; Explains the physical chemistry of various metallurgical steps, such as roasting, matte smelting/converting, and reduction smelting, steelmaking, aqueous processing etc. in extraction of metals; Collects and uniformly presents scattered information on physicochemical principles of metal production from various books and journals.

This book presents several helpful synthetic methods for diverse multinuclear complexes. The results described can be used to selectively connect mononuclear as well as multinuclear complexes with other metal complexes to construct valuable photofunctional compounds. Using the new synthetic methods, it was possible to selectively connect several types of metal complexes in a single step under relatively mild reaction conditions. This so-called building block approach utilizes various C-C coupling reactions between metal complexes with functional groups as active moieties. Owing to the large pi-conjugation systems, the multinuclear complexes synthesized using coupling reactions showed a strong absorption ability over a wide range of visible light and long emission lifetimes, which are ideal properties for photosensitizers and light absorbers. By combining these coupling methods with the newly developed hydrogenation reactions, the binding mode of the linkers in multinuclear complexes can be modified in order to tune the photophysical properties and photocatalytic ability. As such, the synthesized multinuclear complexes can be used for various purposes, e.g., as photocatalysts and photosensitizers, and in light-harvesting systems. The synthetic methods and strategies presented in this book diversify not only the structures but also functions of multinuclear complexes.