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.

Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.

As nucleophiles, simple alkenes are typically so unreactive that only highly active electrophiles, such as carbocations, peroxides, and halogens will react with them. For the generation of carbon-carbon bonds, milder methods will often be required. Fortunately, it is possible to increase the reactivity of alkene-type p-nucleophiles by introducing electron-donating substituents. Substitution of one H with an OH or OR gives an enol or a vinyl ether, which are already much better nucleophiles. Using nitrogen instead of oxygen, one obtains even better nucleophiles, enamines. Enamines are among the most reactive neutral carbon nucleophiles, exhibiting rates that are even comparable to some charged nucleophiles, such as enolates [1, 2]. Most enamines, unfortunately, are sensitive to hydrolysis. The parent enamine, N,N-dimethylvinylamine, has in fact been prepared [3], but appears to be uns- ble. Enamines of cyclic ketones and many aldehydes can readily be isolated, however [4-7]. The instability of enamines might at first appear to diminish the utility of enamines as nucleophiles, but actually this property can be viewed as an added benefit: enamines can be readily and rapidly generated catalytically by using a suitable amine and a carbonyl compound. The condensation of aldehydes or ketones with amines initially affords an imine or iminium ion, which then rapidly loses a proton to afford the corresponding enamine (Scheme 1).

This book investigates the use of palladium modified by bulky ligands as catalysts for new chemical transformations that rapidly assemble several classes of complex heterocyles. It documents the development of new chemical reactions involving carbon-carbon (C-C) and carbon-halogen (C-X) bond formation in the context of alkene difunctionalization and dearomatization reactions. Due to the ubiquity of heterocycles in bioactive natural products and life-improving pharmaceutical treatments, a long-term goal for synthetic organic chemists has been to develop novel and creative heterocycle syntheses that illicit a high degree of product diversity and are characterized by mild reaction conditions and limited waste production. A considerable fraction of leading pharmaceutical drugs contain at least one heterocycle within their chemical structure, and their prevalence in these technologies is strong evidence that the fundamental curiosities of organic chemistry lead to real-world solutions for the health and wellness of the global population.

Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.

This book presents the synthetic methodologies as well as the properties and potential usage of various ruthenium-containing materials. Starting from the first examples of 'ruthenopolymers' reported in the 1970s to the 3D architectures now synthesized, these materials have shown their importance far beyond fundamental polymer science. As well as highlighting the remarkable properties and versatile applications, this book also addresses a key question related to the applications of such heavy-metal-containing materials from the perspective of achieving a sustainable future. This book is of interest to both materials scientists and chemists in academia and industry.

This outstanding thesis describes a detailed investigation into the use of low-oxidation-state group 14 complexes in catalysis, developed at the cutting edge of inorganic and organometallic chemistry. It includes the preparation of a number of landmark compounds, some of which challenge our current understanding of metal-metal bonding and low-oxidation-state main group chemistry. Among the many highlights of this thesis, the standout result is the development of the first well-defined, low- oxidation-state main group hydride systems as highly efficient catalysts in the hydroboration of carbonyl substrates, including carbon dioxide, which are as efficient as those observed in more traditional, transition-metal catalyses. These results essentially define a new subdiscipline of chemistry.

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."

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.

Advances in Polymer Science enjoys a longstanding tradition and good reputation in its community. Each volume is dedicated to a current topic, and each review critically surveys one aspect of that topic, to place it within the context of the volume. The volumes typically summarize the significant developments of the last 5 to 10 years and discuss them critically, presenting selected examples, explaining and illustrating the important principles, and bringing together many important references of primary literature. On that basis, future research directions in the area can be discussed. Advances in Polymer Science volumes thus are important references for every polymer scientist, as well as for other scientists interested in polymer science - as an introduction to a neighboring field, or as a compilation of detailed information for the specialist.

Alexander L. Reznichenko and Kai C. Hultzsch: Catalytic ?-Bond Metathesis Zhichao Zhang, Dongmei Cui, Baoli Wang, Bo Liu, Yi Yang: Polymerization of 1,3-Conjugated Dienes with Lanthanide Precursors Frank T. Edelmann: Homogeneous Catalysis using Lanthanide Amidinates and Guanidinates Tianshu Li, Jelena Jenter, Peter W. Roesky: Rare Earth Metal Post-metallocene Catalysts with Chelating Amido Ligands

This book focuses on the computational modeling of organometallic reactivity. In recent years, computational methods, particularly those based on Density Functional Theory (DFT) have been fully incorporated into the toolbox of organometallic chemists' methods. Nowadays, energy profiles of multistep processes are routinely calculated, and detailed mechanistic pictures of the reactions arise from these calculations. This type of analysis is increasingly performed even by experimentalists themselves. The volume aims to connect established computational organometallics with the more recent theoretical and methodological developments applied to this field. This would allow broadening of the simulation scope toward emergent organometallic areas (as ligand design or photoactivated processes), to narrow the gap between calculations and experiments (microkinetic models) and even to discover new reactions (automated methods). Given the broad interest and extensive application that computational methods have reached within the organometallic community, this new volume will attract the interest of both experimental and computational organometallic chemists.

Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.

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.

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.

Major portion of the planet earth is covered by seas and oceans representing 96.5% of the planet's water, playing a detrimental role in sustaining the plant including crop diversity and productivity for human consumption. Water resources contain both soluble and transition metals, which are easily absorbed by plants through roots as a first point of contact and subsequently play important physiological and biological functions in plants. Transition metals such as copper (Cu), iron (Fe), manganese (Mn) and zinc (Zn) contribute to the plant productivity by playing key functional roles in the photosynthesis. In addition, to their major role in regulating the plant productivity, they also play an important role by acting as homeostatic regulators in uni-parentally inherited chloroplasts and maintains the flow of the electron transfer. It is worthwhile to mention that they play a critical role as transporters, which acts as electron balancing units for managing the electrostatic potential across the membranes. In contrast, some metals such as Cd, As play a significant role in inducing the stress mechanism and influencing either directly or in-directly Haber-Weiss reactions either through the production of the reactive oxygen species (ROS) or through the membrane damage thus leading to leakage of membrane transporters. However, besides playing a detrimental role as transporters in plant system, excessive accumulation of these metals due to the increasing contamination in the marginal soil and water are posing important threats to the plant system. Realizing the toxic effects of the metals, several physiological evidences have been laid for the credence of the metal toxicity and their concurrent effect on plant productivity. Increasing effects of the metals as toxicants can have three adverse effects on the populations: population can move, persist via local adaptation or phenotypic plasticity, or die. Next generation sequencing studies have revolutionized our abilities to detect the changes in expression profiles across an array of genes, which can in-turn help to develop early markers of metal induced stress. Plant Metallomics and Functional Omics: A System-Wide Perspective focuses on the applications of the system wide understanding of the biological and functional interplay occurring at the juncture of the metalloid induced stress and toxicity. The main goal of this book is to familiarize the readers with the most up-to-date information on metal-induced physiological changes in plant species.

This book joins an international and interdisciplinary group of leading experts on the biomedical, energy and environmental applications of Metal-Organic Frameworks (MOFs). The resulting overview covers everything from the environmentally friendly and scale up synthesis of MOFs, their application in green energy generation and storage, and water purification to their use as drug delivery systems, biosensors, and their association with relevant macromolecules (genes, enzymes). This book is focused on the interest of MOFs in applications such as the leading -edge environmental (energy-related) and biomedical fields. The potential of MOFs in these areas is currently progressing at a fast pace, since the wide possibilities that MOFs offer in terms of composition, topology, incorporation of active species (in their porosity, on their external surface or within the framework), and post-synthetic modifications, among others. The aim here is to provide future research goals that emphasize relevant nuances to this class of materials as a whole.

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.

Antoine Simonneau's thesis highlights the development of new cycloisomerization reactions through the activation of alkynes with gold complexes. First Simonneau describes 1,6-enynes and their direct conversion into allenes through 1,5-hydride or ester migration processes. The author and his team used appropriate propargylic functional groups to achieve this conversion. This study shows that O-tethered 1,6-enynes carrying a strained cycloalkane at the propargylic position could undergo a cyclopropanation/ring expansion cascade reaction. The author employed this rearrangement as the starting point in the design of a new macro cycle synthesis. The next part of the thesis focuses on the cycloisomerization of diynes involving as the first step of the process the rearrangement of one alkyne partner into an allene thanks to a gold-catalyzed 1,3-shift of a propargylic ester. The thesis discloses a new cycloisomerization pattern featuring a 1,5-carbonyl transfer, giving rise to unprecedented cross-conjugated diketones. In the final part of the research, Simmoneau investigates the gold-catalyzed cycloisomerization mechanism of 1,6-enynes and questions the intermediacy of gold acetylides. By the means of NMR and mass spectrometry analysis, theoretical treatment and solution experiments, it was possible to rule out the involvement of these species in the catalytic cycle. This thesis has led to a number of publications in high-impact journals.

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.

The manufacture of polyolefins by metallocene catalysts represents a revolution in the polymer industry. The first, patent for a metallocene catalyst was filed in 1980 but it has been the last five years that have seen a dramatic increase in the volume of research into metallocenes and the maturing of metallocene technology. With contributions from leading experts from the US, Canada, Italy, Scandinavia, Germany and Japan, Metallocene-based Polyolefins gives comprehensive coverage of all areas of metallocene technology: catalyst structure, comonomer incorporation, polymerization mechanisms and conditions, reactor configurations, special properties, rheological and processing behaviour, comparison with conventional polyolefins and fields of application. An essential book for plastics engineers, polymer chemists, physicists, materials scientists and all those working in the plastics manufacturing and processing industries.

In this book the authors describe how they reproduced the redox functions of biocatalysts artificially. It includes the introduction and discussion of synthetic reactions via electron transfer, hybrid -conjugated systems, and biorganometallic conjugates as novel redox systems. The work was conducted in pioneering fields based on redox systems, in synthetic organic chemistry, synthetic materials chemistry, and bioorganometallic chemistry. The step-by-step process is illustrated by the three major parts of the book: redox reactions (selective synthetic methods using metal-induced redox reactions), redox systems (design and redox function of conjugated complexes with polyanilines or quinonediimines and molecular bowl sumanene), and design of bioorganometallic conjugates to induce chirality-organized structures (bio-related structurally controlled systems). This systematic and up-to-date description will be of special interest to graduate students who are meeting the new challenges of chemistry, as well as to post-doctoral researchers and other practicing chemists in both academic and industrial settings.

Transition metal catalysis belongs to the most important chemical research areas because a ubiquitous number of chemical reactions are catalyzed by transition metal compounds. Many efforts are being made by industry and academia to find new and more efficient catalysts for chemical processes. Transition metals play a prominent role in catalytic research because they have been proven to show an enormous diversity in lowering the activation barrier for chemical reactions. For many years, the search for new catalysts was carried out by trial and error, which was costly and time consuming. The understanding of the mechanism of the catalytic process is often not very advanced because it is difficult to study the elementary steps of the catalysis with experimental techniques. The development of modern quantum chemical methods for calculating possible intermediates and transition states was a breakthrough in gaining an understanding of the reaction pathways of transition metal catalyzed reactions. This volume, organized into eight chapters written by leading scientists in the field, illustrates the progress made during the last decade. The reader will obtain a deep insight into the present state of quantum chemical research in transition metal catalysis.

This book is a comprehensive text covering the research and development trends in the booming field of transition metal catalyzed oxidative cross-coupling reactions. Oxidative cross-coupling reaction is a new method to forming chemical bonds besides the traditional cross-coupling reactions. This book provides the answers to how this coupling reaction occurs and what its advantages are. The palladium, copper and iron catalyzed oxidative cross-coupling reactions as the main focuses of interest are described in detail. The oxidative cross-coupling reactions catalyzed by other metals and transition-metal-free oxidative coupling reactions are also introduced.This book provides a useful reference source for researchers and graduates in the field of transition metal catalyzed coupling reactions. It is also valuable to researchers working in pharmaceutical companies, fine organic chemical companies, and etc.

Spectroscopic Properties of Inorganic and Organometallic Compounds provides a unique source of information on an important area of chemistry. Divided into sections mainly according to the particular spectroscopic technique used, coverage in each volume includes: NMR (with reference to stereochemistry, dynamic systems, paramagnetic complexes, solid state NMR and Groups 13-18); nuclear quadrupole resonance spectroscopy; vibrational spectroscopy of main group and transition element compounds and coordinated ligands; and electron diffraction. Reflecting the growing volume of published work in this field, researchers will find this Specialist Periodical Report an invaluable source of information on current methods and applications. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading experts in their specialist fields, this series is designed to help the chemistry community keep current with the latest developments in their field. Each volume in the series is published either annually or biennially and is a superb reference point for researchers. www.rsc.org/spr