This book presents an in-depth study into the utility of -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 -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 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.

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 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.

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.

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.

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.

This is the first book to comprehensively address the recent developments in both the experimental and theoretical aspects of quasi-one-dimensional halogen-bridged mono- (MX) and binuclear metal (MMX) chain complexes of Pt, Pd and Ni. These complexes have one-dimensional electronic structures, which cause the various physical properties as well as electronic structures. In most MX-chain complexes, the Pt and Pd units are in M(II)-M(IV) mixed valence or charge density wave (CDW) states due to electron-phonon interactions, and Ni compounds are in Ni(III) averaged valence or Mott-Hubbard states due to the on-site Coulomb repulsion. More recently, Pd(III) Mott-Hubbard (MH) states have been realized in the ground state by using the chemical pressure. Pt and Pd chain complexes undergo photo-induced phase transitions from CDW to MH or metal states, and Ni chain complexes undergo photo-induced phase transitions from MH to metal states. Ni chain complexes with strong electron correlations show tremendous third-order optical nonlinearity and nonlinear electrical conductivities. They can be explained theoretically by using the extended Peierls-Hubbard model. For MMX-chain complexes, averaged valence, CDW, charge polarization, and alternating charge polarization states have been realized by using chemical modification and external stimuli, such as temperature, photo-irradiation, pressure, and water vapor. All of the electronic structures and phase transitions can be explained theoretically.

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.

This book presents critical reviews of the present position and future trends in modern chemical research concerned with chemical structure and bonding. It contains short and concise reports, each written by the world's renowned experts. Still valid and useful after 5 or 10 years, more information as well as the electronic version of the whole content available at springerlink.com.

Heterogeneous Enantioselective Hydrogenation: Theory and Practice reviews the development of enantioselective hydrogenation reaction catalysts. It looks at the first relatively ineffective catalysts right through to modern highly effective enantioselective catalytic systems, comparable in their efficiency to chiral metal complexes and enzymatic systems. The book begins with a summary of the first work on heterogeneous metal catalysts, which showed only the principal possibilities of enantioselective reactions. It then elaborates on metal catalysts which have enantioselectivities close to 100%. Finally, the practical utilization of chiral catalytic systems in processes of hydrogenation is described. The alpha- and beta-hydroxy carboxylic acid esters produced are precursors for manufacturing many synthones used for medicines as well as for monomers used for biodegradable polyesters, both of which have important practical applications. The volume summarizes more than 800 scientific papers in the field of enantioselective catalytic hydrogenation reactions, mainly those using heterogeneous metal catalysts. It provides detailed explanations of special techniques for the preparation of effective dissymmetric catalysts which provide highly efficient catalytic systems.

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.

Our knowledge of the chemistry of selenium and tellurium has seen significant progress in the last few decades. This monograph comprises contributions from leading scientists on the latest research into the synthesis, structure and bonding of novel selenium and tellurium compounds. It provides insight into mechanistic studies of these compounds and describes coordination chemistry involving selenium and tellurium containing ligands. Contributions also describe the theoretical and spectroscopic studies of selenium and tellurium compounds. Additionally, this monograph outlines the applications of selenium and tellurium in biological systems, materials science and as reagents in organic synthesis and shows how these applications have been a fundamental driving force behind the research into the inorganic and organic chemistry these fascinating elements.

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.

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.

V.W.-W. Yam, K.M.-C. Wong: Luminescent Molecular Rods - Transition Metal Alkynyl Complexes.- D.K. James, M. Tour: Molecular Wires.- C. Chiorboli, M.T. Indelli, F. Scandola: Photoinduced Electron/Energy Transfer Across Molecular Bridges in Binuclear Metal Complexes.- E.A. Weiss, M.R. Wasielewski, M.A. Ratner: Molecules as Wires: Molecule-Assisted Movement of Charge and Energy.- F.C. Grozema, L.D.A. Siebbeles, G.H. Gelinck, J.M. Warman: The Opto-Electronic Properties of Isolated Phenylenevinylene Molecular Wires

Silicones have unique properties including thermal oxidative stability, low temperature flow, high compressibility, low surface tension, hydrophobicity and electric properties. These special properties have encouraged the exploration of alternative synthetic routes of well defined controlled microstructures of silicone copolymers, the subject of this Springer Brief. The authors explore the synthesis and characterization of notable block copolymers. Recent advances in controlled radical polymerization techniques leading to the facile synthesis of well-defined silicon based thermo reversible block copolymers are described along with atom transfer radical polymerization (ATRP), a technique utilized to develop well-defined functional thermo reversible block copolymers. The brief also focuses on Polyrotaxanes and their great potential as stimulus-responsive materials which produce poly (dimethyl siloxane) (PDMS) based thermo reversible block copolymers.

Metal ions in the brain are a necessity as well as a poison. The presence of metal ions in the active sites of biological catalysts or metalloproteins and in the biological functioning of nucleic acids is very well documented and they are required for brain activity. On the other hand, metals are very effective in generating oxidative stress. This effect does not only play a role in immunology but also is the root of practically all neurodegenerative disorders by inducing disease via the death of neurons. Managing metal ions in the brain could therefore be an important strategy in the search for therapeutic agents used in the treatment of neurodegenerative diseases. This new title gives an overview to key topics in the area of metal ions in the brain. It focuses on the role of metal ions in neurological systems by describing their advantageous functions as well as their poisonous features. It is therefore of interest for scientists in biochemistry and biophysics, physiology, toxicology as well as for physicians focused on this topic.

T. L.S. Kishbaugh: Metalation of Pyrrole.- K.-S. Yeung: Furans and Benzofurans.- P. E. Alford: Lithiation-Based and Magnesation-Based Strategies for the Functionalization of Imidazole: 2001-2010.- L. Fu: Metalation of Oxazoles and Benzoxazoles.- S. Roy * S. Roy * G. W. Gribble: Metalation of Pyrazoles and Indazoles.- J. C. Badenock: Metalation Reactions of Isoxazoles and Benzisoxazoles.- Y.-J. Wu: Thiazoles and Benzothiazoles.- C. F. Nutaitis: Isothiazoles and Benzisothiazoles.- E. R. Biehl: Recent Advances in the Synthesis of Thiophenes and Benzothiophenes.- J. M. Lopchuk: Mesoionics.- J. M. Lopchuk: Azoles with 3-4 Heteroatoms.

In order to meet the ever-increasing demands for enantiopure compounds, heteroge- ous, homogeneous and enzymatic catalysis evolved independently in the past. Although all three approaches have yielded industrially viable processes, the latter two are the most widely used and can be regarded as complementary in many respects. Despite the progress in structural, computational and mechanistic studies, however, to date there is no universal recipe for the optimization of catalytic processes. Thus, a trial-and-error approach remains predominant in catalyst discovery and optimization. With the aim of complementing the well-established fields of homogeneous and enzymatic catalysis, organocatalysis and artificial metalloenzymes have enjoyed a recent revival. Artificial metalloenzymes, which are the focus of this book, result from comb- ing an active but unselective organometallic moiety with a macromolecular host. Kaiser and Whitesides suggested the possibility of creating artificial metallo- zymes as long ago as the late 1970s. However, there was a widespread belief that proteins and organometallic catalysts were incompatible with each other. This severely hampered research in this area at the interface between homogeneous and enzymatic catalysis. Since 2000, however, there has been a growing interest in the field of artificial metalloenzymes for enantioselective catalysis. The current state of the art and the potential for future development are p- sented in five well-balanced chapters. G. Roelfes, B. Feringa et al. summarize research relying on DNA as a macromolecular host for enantioselective catalysis.

Valentine P. Ananikov, Irina P. Beletskaya: Alkyne and alkene insertion into metal-heteroatom and metal-hydrogen bonds - the key stages of hydrofunctionalization process.- Akihiko Ishii* and Norio Nakata: The Mechanism for Transition Metal-Catalyzed Hydrochalcogenation of Unsaturated Organic Molecules.- A. L. Reznichenko and Kai C. Hultzsch: Early Transition Metal (Group 3-5, Lanthanides and Actinides) and Main Group Metal (Group 1, 2, and 13) Catalyzed Hydroamination.- Naoko Nishina and Yoshinori Yamamoto: Late transition metal catalyzed hydroamination.- Sumod A. Pullarkat and Pak-Hing Leung: Chiral Metal Complex Promoted Asymmetric Hydrophosphinations.- Masato Tanaka: Recent Progress in Transition Metal-Catalyzed Addition Reactions of H-P(O) Compounds with Unsaturated Carbon Linkages.- Christian Bruneau: Group 8 metals-catalyzed O-H bond addition to unsaturated molecules.- Giorgio Abbiati, Egle M. Beccalli, Elisabetta Rossi: Groups 9 and 10 metals-catalyzed O-H bond addition to unsaturated molecules.- Nuria Huguet and Antonio M. Echavarren: Gold-Catalyzed O-H Bond Addition to Unsaturated Organic Molecules.- Akiya Ogawa: Transition-Metal-Catalyzed S-H and Se-H Bonds Addition to Unsaturated Molecules.

Johannes G. de Vries: Pd-catalyzed coupling reactions.- Gregory T. Whiteker and Christopher J. Cobley: Applications of Rhodium-Catalyzed Hydroformylation in the Pharmaceutical, Agrochemical and Fragrance Industries.- Philippe Dupau: Ruthenium-catalyzed Selective Hydrogenation for Flavor and Fragrance Applications.- Hans-Ulrich Blaser, Benoit Pugin and Felix Spindler: Asymmetric Hydrogenation.- Ioannis Houpis: Case Study: Sequential Pd-catalyzed Cross-Coupling Reactions; Challenges on Scale-up.- Adriano F. Indolese: Pilot Plant Scale Synthesis of an Aryl-Indole - Scale up of a Suzuki Coupling.- Per Ryberg: Development of a Mild and Robust Method for Palladium Catalysed Cyanation on Large Scale.- Cheng-yi Chen: Application of Ring Closing Metathesis Strategy to the Synthesis of Vaniprevir (MK-7009), a 20-Membered Macrocyclic HCV Protease Inhibitor.

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.