This volume covers both basic and advanced aspects of organometallic chemistry of all metals and catalysis. In order to present a comprehensive view of the subject, it provides broad coverage of organometallic chemistry itself. The catalysis section includes the challenging activation and fictionalization of the main classes of hydrocarbons and the industrially crucial heterogeneous catalysis. Summaries and exercises are provides at the end of each chapter, and the answers to these exercises can be found at the back of the book. Beginners in inorganic, organic and organometallic chemistry, as well as advanced scholars and chemists from academia and industry will find much value in this title.

The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus 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 should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.

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.

For several years, the two parallel worlds of Molecular Conductors in one hand and Molecular Magnetism in the other have grown side by side, the former essentially based on radical organic molecules, the latter essentially based on the high spin properties of metal complexes. Over the last few years however, organometallic derivatives have started to play an increasingly important role in both worlds, and have in many ways contributed to open several passages between these two worlds. This volume recognizes this important emerging evolution of both research areas. It is not intended to give a comprehensive view of all possible organometallic materials, and polymers for example were not considered here. Rather we present a selection of the most recent research topics where organometallic derivatives were shown to play a crucial role in the setting of conducting and/or magnetic properties in crystalline materials. First, the role of organometallic anions in tet- thiafulvalenium-based molecular conductors is highlighted by Schlueter, while Kubo and Kato describe very recent ortho-metalated chelating ligands appended to the TTF core and their conducting salts. The combination of conducting and magnetic properties and the search for p-d interactions are analyzed in two comp- mentary contributions by Myazaki and Ouahab, while Valade focuses on the only class of metal bis(dithiolene) complexes to give rise to superconductive molecular materials, in association with organic as well as organometallic cations.

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.

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.

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.

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.

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

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.

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.

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.

Organometallic Ion Chemistry features eight chapters, written by acknowledged authorities, covering the gas-phase chemistry of organometallic ions. Topics covered include: periodic trends in gas-phase thermochemistry of transition metal-ligand systems; ab initio calculations to determine electronic structure, geometric structure, and thermochemistry of metal-containing systems; electronic state effects on metal ion reactivity; organometallic ion photochemistry; applications of gas-phase electron transfer equilibria in organometallic redox thermochemistry. Also included are state of the art mass spectrometric instrumentation used in such studies. Finally, the book features - for the first time in one place - a comprehensive list (containing over 1500 entries) of metal ion-ligand bond energies, obtained from theory and experiment. An invaluable reference source for ion chemists, organometallic chemists and surface chemists, at both expert and graduate student levels.

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.

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.

Lucas Montero de Espinosa and Michael A. R. Meier: Olefin Metathesis of Renewable Platform Chemicals.- Pieter C. A. Bruijnincx, Robin Jastrzebski, Peter J. C. Hausoul, Robertus J. M. Klein Gebbink, and Bert M. Weckhuysen: Pd-Catalysed Telomerisation of 1,3-Dienes with Multifunctional Renewable Substrates - Versatile Routes for the Valorisation of Biomass-Derived Platform Molecules.- A Behr, A. J. Vorholt: Hydroformylation and related reactions of renewable resources.- Ties J. Korstanje, Robertus J.M. Klein Gebbink: Catalytic oxidation and deoxygenation of renewables with rhenium complexes.- Antoine Buchard, Clare M. Bakewell, Jonathan Weiner and Charlotte K. Williams: Recent Developments In Catalytic Activation Of Renewable Resources For Polymer Synthesis.

Janusz Lewinski and Andrew E. H. Wheatley: Simple trivalent organoaluminum species: perspectives on structure, bonding and reactivity.- Stephan Schulz: Organoaluminum complexes with bonds to s-block, p-block, d-block, and f-block metal centers.- Samuel Dagorne and Christophe Fliedel: Low valent organoaluminium (+I, +II) species.- Rudolf Wehmschulte: Organoaluminum species in homogeneous polymerization catalysis.- Paul Knochel, Tobias Blumke, Klaus Groll and Yi-Hung Chen: Preparation of Organoalanes for Organic Synthesis.- Yuki Naganawa and Keiji Maruoka: Reactions Triggered by Lewis Acidic Organoaluminum Species.- Usein M. Dzhemilev and Vladimir A. D'yakonov: Hydro-, Carbo- and Cycloalumination of Unsaturated Compounds.- Andreas Kolb and Paultheo von Zezschwitz: Organoaluminum Couplings to Carbonyls, Imines and Halides.- Oscar Pamies and Montserrat Dieguez: Conjugate Addition of Organoaluminum Species to Michael Acceptors and Related Processes.

Gerard van Koten: The Mono-anionic ECE-Pincer Ligand - a Versatile Privileged Ligand Platform: General Considerations.- Elena Poverenov, David Milstein: Non-Innocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes.- Dean M. Roddick: Tuning of PCP Pincer Ligand Electronic and Steric Properties.- Gemma R. Freeman, J. A. Gareth Williams: Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and Luminescence.- Davit Zargarian, Annie Castonguay, Denis M. Spasyuk: ECE-Type Pincer Complexes of Nickel.- Roman Jambor and Libor Dostal: The Chemistry of Pincer Complexes of 13 - 15 Main Group Elements.- Kalman J. Szabo: Pincer Complexes as Catalysts in Organic Chemistry.- Jun-ichi Ito and Hisao Nishiyama: Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multi-potent Catalysts.- Anthony St. John, Karen I. Goldberg, and D. Michael Heinekey: Pincer Complexes as Catalysts for Amine Borane Dehydrogenation.- Dmitri Gelman and Ronit Romm: PC(sp3)P Transition Metal Pincer Complexes: Properties and Catalytic Applications.- Jennifer Hawk and Steve Craig: Physical Applications of Pincer Complexes.

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.

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.

Giovanni Poli, Guillaume Prestat, Frederic Liron, Claire Kammerer-Pentier: Selectivity in Palladium Catalyzed Allylic Substitution.- Jonatan Kleimark and Per-Ola Norrby: Computational Insights into Palladium-mediated Allylic Substitution Reactions.- Ludovic Milhau, Patrick J. Guiry: Palladium-catalyzed enantioselective allylic substitution.- Wen-Bo Liu, Ji-Bao Xia, Shu-Li You: Iridium-Catalyzed Asymmetric Allylic Substitutions.- Christina Moberg: Molybdenum- and Tungsten-Catalyzed Enantioselective Allylic Substitutions.- Jean-Baptiste Langlois, Alexandre Alexakis: Copper-catalyzed enantioselective allylic substitution.- Jeanne-Marie Begouin, Johannes E. M. N. Klein, Daniel Weickmann, B. Plietker: Allylic Substitutions Catalyzed by Miscellaneous Metals.- Barry M. Trost, Matthew L. Crawley: Enantioselective Allylic Substitutions in Natural Product Synthesis.

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.

Organolithium chemistry occupies a central position in the selective construction of C-C bonds in both simple and complex molecules. Paralleling the surge of interest in methods for asymmetric synthesis, the use of organolithiums in enantioselective synthesis has witnessed spectacular advances in a little over a decade. This volume is the first dedicated to a comprehensive coverage of this important area. It is designed to provide graduate students and researchers with a rich source of essential information on synthesising molecules in an enantioselective manner using organolithiums, and be an inspiration for future developments. Following an overview chapter summarising the key milestones, successive chapters, each written by leading experts in their field, critically survey all the major areas of progress.

to thank Messrs J. R. Sanders, W. E. Lindsell and M. G. Swanwick for helping to check the text and references and prepare indexes. Finally, I should like to thank my wife for the very considerable assis tance she has given me in the writing and production of this book. M. L. H. G. Contents Preface to the Third Edition, Volume Two Page v INTRODUCTION TO VOLUME TWO I Oassification I The IS-electron rule 2 (i) The basis of the I8-electron rule p. 4, (ii) Exceptions to the I8-electron rule p. 5 1. TWO-ELECTRON LIGANDS 7 A. Classification 7 B. The preparation of olefin-transition metal complexes 7 (a) Displacement of solvent ligands p. 9, (b) Preparations from metal carbonyls p. 9, (c) Less common preparative routes p. 11, Reductive olefination method p. 12 C. A molecular orbital description of the bonding in orga- metallic complexes 13 (a) General comments p. 13, (b) Symmetry considerations p. 13, (c) Energies of the molecular orbitals p. 14 D. A description of the bonding of 2-electron ligands to transition metals 14 E. General comments of 2-electron ligands 19 (a) Infrared studies p. 20, (b) Effect of olefin substituents p. 21, (c) The rotation of ethylene about the ligand-metal bond p. 22, (d) Chemical properties p. 23 F. Particular complexes of metals with 2-electron ligands 25 (a) Copper, silver and gold p. 25, Complexes with benzene p. 28, (b) Nickel, palladium and platinum p."