The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors. All chapters from Topics in Organometallic Chemistry are published OnlineFirst with an individual DOI. In references, Topics in Organometallic Chemistry is abbreviated as Top Organomet Chem and cited as a journal.

This book cuts across the divisions of organic, inorganic, and physical chemistry. It describes new methods for creating -conjugated porphyrin oligomers with precisely defined sequences of zinc and copper metal cations, and how EPR spectroscopy was used to investigate the dipolar and exchange coupling between the paramagnetic copper(II) centres. Porphyrins are a group of heterocyclic macrocycle organic compounds that play an important role in our everyday life and can for example be found in blood where they form a red complex with iron (haem). Various metallic elements can be inserted into a porphyrin and changing the coordinated metal is an excellent way to influence the chemical and physical properties of these molecules. Focusing on 3 metals - zinc, magnesium and copper - the author established new methods for creating -conjugated porphyrin oligomers and lastly presents the synthesis and investigation of two novel porphyrin nanoballs. Giving the template-directed strategy the author developed for constructing these molecules, this work could provide access to other related nano-cages.

Advances in Bioorganometallic Chemistry examines the synthesis, structure and reactivity of bioorganometallics, their pharmaceutical applications, hydrogenase, vitamin B12-like systems, and metalloproteins. It is written by the top researchers in the field and compiled by editors Toshikazu Hirao and Toshiyuki Moriuchi. Developments in this new field of bioorganometallic chemistry, a hybrid between biology and organometallic chemistry, happen very quickly and this comprehensive reference offers the latest research and findings in the field. The book features a discussion of the synthesis, structure, and reactivity of bioorganometallics, and an examination of hydrogenase-like systems, which were designed to demonstrate catalytic activities and functional properties. Advances in Bioorganometallic Chemistry also includes a discussion of bioorganometallics as they relate to medicinal chemistry, specifically applications of metalloproteins, metalloenzymes, and applications in bioimaging. The book concludes with coverage of vitamin B12-like systems, including the latest developments in derivatives designed to perform bio-inspired catalytic reactions. This work is a valuable resource for chemists working in organometallic chemistry and biology, including biochemists, bioorganic chemists, bioinorganic chemists, as well as pharmaceutical scientists, medicinal chemists, and students studying in these areas. Representative authors: R. H. Fish, T. Moriuchi, T. Hirao, H.-B. Kraatz, H. Takaya, T. P. Curran, G. van Koten. E. Rosenberg, J. M. Lynam, C. G. Hartinger, U. Schatzschneider, G. S. Smith, R. Alberto, S. Takenaka, T. Ihara, T. Hayashi, T. Ueno, P. Schollhammer, Y. Shomura, Y. Hisaeda, H. Shimakoshi, B. Krautler

This book provides a detailed description of photofunctionalization of molecular switch based on pyrimidine ring rotational isomerization in copper complexes bearing two bidentate ligands. The most important features of this work focus on the properties associated with the rotational isomerization based on the two possible coordination geometries at the copper center derived from two nitrogen atoms on the unsymmetrically substituted pyrimidine ring. The functions of systems such as dual emission and redox potential switching based on photo-driven rotation will be of particular interest to readers. Both the functions and the procedures for proving these phenomena are beneficial for the development of more functionalized systems based on material science, molecular science, nanoscience, nanotechnology, electrochemistry, photochemistry, coordination chemistry, physical chemistry, and related disciplines. The finding elucidated here holds promise for handling the photoprocesses of metal complexes, valid for both applications and novel properties. This system is expected make it possible to extract an electrochemical potential response from molecular switches, aiming to simulate the five senses of human beings at a single molecular level.

Adi Haber's thesis summarises the use of a new entity, the corrole, to combat one of the major cardiovascular diseases, atherosclerosis. She examines the effects of three rationally designed corrole-metal complexes on some of the many variables which contribute to the development of atherosclerosis. There is a focus on both the "bad" and "good" cholesterol carriers, LDL and HDL. Adi Haber proceeds from basic findings in pure chemistry through biochemical and cell culture tests to in vivo examinations. The work in this thesis shows that corroles are highly efficient both for early and late treatment of atherosclerosis in animals. These results will pave the way for ongoing regulated preclinical studies focussed on the development of metallocorroles as potential drugs for treating cardiovascular diseases.

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.

This textbook addresses the chemical and physicochemical principles of supramolecular host-guest chemistry in solution. It covers the thermodynamics and dynamics of inclusion and highlights several types of organic hosts. Various applications of host-guest chemistry in analytical and environmental chemistry as well as pharmaceutical and chemical industry demonstrate the versatile usability of molecular cages.

With contributions from leading international experts, this essential book gives comprehensive coverage of all areas of metallocene catalysts and metallocene-based polyolefins including details of the very latest developments.
The manufacture of polyolefins by metallocene catalysts represents a revolution in the polymer industry. The last five years in particular have seen a dramatic increase in the volume of research into metallocenes and the maturing of metallocene technology.
The following areas are covered in this comprehensive book: catalyst structure, comonomer incorporation, polymerization mechanisms and conditions, reactor configurations, special properties, comparison with conventional polyolefins, rheological and processing behavior and fields of application.
This is an invaluable book for plastics engineers, polymer chemists, physicists, materials scientists, and all those working in the plastics manufacturing and processing industries.

This comprehensive reference/text provides a "how-to" approach to the Demonstrates cutting-edge applications in actinide chemistry, catalysi Written by leading researchers in the field, Computational Organometal lic Chemistry is an outstanding reference for organometallic, computat ional, inorganic, organic, medicinal, and materials chemists; and indu strial researchers; and an invaluable and informative text for upper-l evel undergraduate and graduate students in these disciplines.

Bioorganometallic Chemistry is an excellent introduction to this transdisciplinary field which is straddled with biochemistry, medicine and organometallic chemistry. The book is a comprehensive review on the latest advances of this rapidly growing area, as well as historical background and future trends, revealing a tremendous potential of bioorganometallic compounds as novel drug candidates and diagnostic tools.

Synthesis of Carbon-Phosphorus Bonds, Second Edition is a working guide for the laboratory, incorporating classical approaches with the recent developments of carbon-phosphorus (C-P) bond formation. These advances include the preparation of phosphoranes -- specifically in the use of transient oxophosphoranes as intermediates in organophosphorus compound synthesis - along with the new approaches towards the preparation of compounds with aromatic and vinylic C-P bonds.

Synthesis of Carbon-Phosphorus Bonds, Second Edition serves as a useful tool in the laboratory. It offers detailed surveys of IUPAC nomenclature recommendations, common notation systems, and various experimental examples. These features help to make this text an effective source of critical and annotated references, as well as a a working guide for organic and phosphorus chemists specifically, or for any chemists working with C-P bonds.

Ana Escribano Cuesta's thesis presents a detailed study of the inter- and intramolecular reactions of carbonyl compounds with 1,6 -enynes using gold (I) complexes. An important part of the work involved streamlining the variables that allow the selective synthesis of different products such as tricyclic compounds, dihydropyrans, 1,3-dienes or cyclobutenes. The second chapter highlights the importance and difficulties in synthesising a cyclobutene subunit and the author includes a detailed description of how the products were prepared. The final chapter outlines the synthesis of lundurines using methodology developed by the author's research group for intramolecular gold-catalyzed cyclization of indoles with alkynes. The lundurine products developed in this work show significant in vitro cytoxicity toward B16 melanoma cells. The work in this thesis has led to a number of publications in high- profile chemistry journals.

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

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 with 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 has 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.

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 presents an in-depth study into the utility of σ-bond metathesis in Group 2 mediated reactivity. A comprehensive introduction defines the state of the art in both Group 2 mediated catalysis and dehydrocoupling. Structural investigations giving rise to a range of mixed s-block metal hydrides including a remarkable dodecabimetallic decahydride are then described. Subsequent extensive mechanistic work focussing on both silicon-nitrogen and boron-nitrogen dehydrocoupling gives insights into both congeneric effects down Group 2 and ligand effects centring upon magnesium. These studies show the striking effects of these factors, as well as the electronic nature of the hydridic coupling partner.  Finally, the unprecedented introduction of single-electron transfer steps into Group 2 catalytic manifolds is described. The use of the stable radical TEMPO to induce single-electron transfer to substituents bound to Group 2 centres coupled with σ-bond metathesis allows a novel hydrogen release from silanes.

This thesis addresses the coordination chemistry and reactivity of copper and gold complexes with a focus on the elucidation of (i) the metal-mediated activation of -bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but remain elusive for Cu and Au complexes. In this work, the author contributes significant advances: The first -SiH complexes of copper are experimentally and computationally characterized, yielding valuable insights into -bond activation processes for copper. Evidence for a highly unusual migratory syn insertion of unsaturated organic molecules into the gold-silicon bond of silylgold (I) complexes is provided and the corresponding mechanism identified. The intermolecular oxidative addition of -SiSi, -CC and -CX (X=halogen) bonds with molecular gold (I) complexes is studied in detail, effectively demonstrating that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. The use of small-bite angle bis (phosphine) gold (I) complexes allows for the first time the oxidative addition of -CC and -CX bonds for gold (I). These results shed light on an unexpected reactivity pattern of gold complexes and may point the way to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors. All chapters from Topics in Organometallic Chemistry are published OnlineFirst with an individual DOI. In references, Topics in Organometallic Chemistry is abbreviated as Top Organomet Chem and cited as a journal

The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field. Review articles for the individual volumes are invited by the volume editors. Readership: research chemists at universities or in industry, graduate students.

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

This book extends the development of the thermodynamic theory of specific intermolecular interactions to element-organic and specific organometallic compounds. The fundamentals of an unconventional approach to the theory of H-bonding and specific interactions are formulated, based on a concept of pentacoordinate carbon atoms. Prof. Baev has introduced the theory already in his successful books "Specific Intermolecular Interactions of Organic Compounds" and "Specific Intermolecular Interactions of Nitrogenated and Bioorganic Compounds". In this book he also demonstrates it for element organic and specific organometallic compounds, a class of substances which is of great importance in synthetic chemistry and catalysis. Furthermore, organic compound classes, that have not been treated in the previous books, are included. New types of hydrogen bonds and specific interactions are substantiated and their energies are determined on the basis of the developed methodology. In this way, the influence of the molecular structure on the energy and on intermolecular interactions can be discussed for these particular compound classes.

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.

The application of molecules in technological devices hinges on the proper understanding of their behavior on metallic electrodes or substrates. The intrinsic molecular electronic and magnetic properties are modified at a metallic interface, and greatly depend on the atomic configuration of the molecule-metal bond. This poses certain problems, such as the lack of reproducibility in the transport properties of molecular junctions, but also offers the possibility to induce new charge and spin configurations that are only present at the interface. The results presented in this thesis address this issue, providing a comprehensive overview of the influence of molecule-metal and molecule-molecule interactions on the electronic and magnetic properties of molecules adsorbed on metallic substrates. Using metal-phthalocyanines (MePc), a commonly used metal-organic complex as a model system, each chapter explores different aspects of the interaction with silver surfaces: the local adsorption geometry, self-assembly, the modifications of the electronic and magnetic characteristics due to hybridization and charge transfer, and finally the manipulation of molecular charge and spin states by electron doping using alkali atoms moved with the STM tip.

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics in pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.

In this thesis, the author introduces two strategies used to construct various types of N-heterocycles, based on the chemistry of zirconacycles and 2,6-diazasemibullvalenes. In the first part, the author presents the development of multi-component cyclization of a zirconacyclobutene-silacyclobutene fused compound, nitriles and unsaturated compounds. These reactions provide synthetically useful methodology for various N-heterocycles such as 3-acyl pyrrole, pyrrolo[3,2-d]pyridazine and dihydropyrroloazepine, which are all difficult to synthesize by other means. The isolation and characterization of the key three-fused-ring Zr/Si-containing intermediates are also described in detail. These results show that the zirconacyclobutene-silacyclobutene fused compound behaves as a "chemical transformer" upon treatment with various substrates via the "coordination-induced skeleton rearrangement" mechanism. In the second part, the author demonstrates the synthesis and isolation of a series of 2,6-diazasemibullvalenes (NSBVs) from the reaction of 1,4-dilithio-1,3-dienes and nitriles, highlighting the significant progress made for the first time in this work: (1) determination of X-ray crystal structure of a substituted 2,6-diazasemibullvalene; (2) measurement of the activation barrier of its rapid intramolecular aza-Cope rearrangement in solution; (3) exploration of several reaction types of NSBV with diverse ring-expansion products and "bowl-shape" or "cage-shape" N-containing polycyclic skeletons; (4) demonstration of the localized structure as the predominant form and the homoaromatic delocalized structure as a minor component in the equilibrium using theoretical analysis. Based on well-founded results, this work sheds new light on this controversial topic.