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Books > Science & Mathematics > Chemistry > Organic chemistry > Organometallic chemistry
This book highlights major achievements made in the last five years concerning sustainable C(sp3)-H bond functionalization and offers a promising and emerging tool-kit for organic synthesis. The book is divided into three chapters demonstrating key advances in C(sp3)-H bond functionalization. Chapter 1 reviews transition-metal-catalyzed C(sp3)-H bond functionalization using different directing groups, while Chapter 2 addresses the new methods of transition-metal-catalyzed and metal-free C(sp3)-H bond functionalization without directing groups, in addition to briefly highlighting redox-neutral C(sp3)-H bond functionalization. In closing, Chapter 3 examines visible-light photoredox catalysis, an emerging and highly sustainable C(sp3)-H bond functionalization strategy. The book offers an intriguing and useful reference guide for a broad readership working and/or interested in the fields of organic, organometallic, and green chemistry.
An up-to-date, comprehensive guide to LITHIUM CHEMISTRY
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.
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.
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.
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.
This compilation provides advanced graduate students and researchers with a structured overview of olefin polymerization. Divided into eight chapters written by international experts, this book covers polymerization using various organotransition-metal catalysts, including early and late transition metal complexes, new trends in olefin oligomerization and related reactions. All authors address the historic and scientific backgrounds of the field as well as current research progress and potential for further research. The complete book is designed to present eight independent lectures and, because all authors are well versed in organometallic chemistry, each is based on a profound understanding of the reactions and structures of organotransition metal complexes. This book is an ideal accompaniment for researchers taking courses in olefin polymerization and also serves as a valuable resource for teachers and lecturers of chemistry when planning and researching material for advanced lecture courses.
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.
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.
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.
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.
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.
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.
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.
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.
While the organometallic chemistry of the d-block transition elements has been a flourishing field for the past 25 years, it has only been in the last several years that dramatic activity and progJ'ess has occurred in the area of lanthanide and actinide organometallic chemistry. The f. -element organometallic research effort has been truly multinational and multidisciplinary. In a large number of countries, sCientists have become increasingly interested in the synthesis, reactivity, spectroscopy, and the molecular and electronic structures of f-element organometallic compounds. The backgrounds of these scientists range from organic, inorganic, nuclear, and catalytic chemistry to chemical and nuclear physics. The motivations for the study of f-element organometallics have been equally varied. In the area of basic research, there has been a growing realization that the lanthanides and actinides represent two unique and, to a great extent, neglected families of elements in which many fascinating aspects of chemistry and bonding remain to be explored. On a more practical level, an increasing number of these elements play important roles in nuclear energy production and in industrial catalytic processes. It has become apparent that efficiency and safety in both areas could greatly benefit from increased knowledge. In the past there has been no suitable international forum available for bringing together researchers in the diverse areas of f-element organometallic science mentioned above.
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
Bismuth Catalysts in Aqueous Media, by Shu Kobayashi, Masaharu Ueno and Taku Kitanosono.- Pentavalent Organobismuth Reagents in Organic Synthesis: Alkylation, Alcohol Oxidation and Cationic Photopolymerization , by Yoshihiro Matano.- Environmentally Friendly Organic Synthesis Using Bismuth(III) Compounds, by Scott W. Krabbe and Ram S. Mohan.- Bismuth-Catalyzed Addition of Silyl Nucleophiles to Carbonyl Compounds and Imines, by Thierry Ollevier.- Bismuth Salts in Catalytic Alkylation Reactions, by Magnus Rueping and Boris J. Nachtsheim.- New Applications for Bismuth(III) Salts in Organic Synthesis: From Bulk Chemicals to Steroid and Terpene Chemistry, by J. A. R. Salvador, S. M. Silvestre, R. M. A. Pinto, R. C. Santos and C. Le Roux.- Cationic Bismuth-Catalyzed Hydroamination and Direct Substitution of the Hydroxy Group in Alcohols with Amides, by Shigeki Matsunaga and Masakatsu Shibasaki.- Transition-Metal Catalyzed C-C Bond Formation Using Organobismuth Compounds, by Shigeru Shimada and Maddali L. N. Rao.- Bismuth(III) Salts as Synthetic Tools in Organic Transformations, by J. S. Yadav, Aneesh Antony and Basi V. Subba Reddy.
Organometallic chemistry explores the chemistry of the often bewildering variety of compounds featuring metal-carbon bonds. A field that has underpinned the development of new synthetic methods and materials, it is also central to our understanding of catalysis. In his text, Manfred Bochmann distils the extensive knowledge of the field into a succinct overview of essential concepts. The book is enriched throughout with examples that demonstrate how our understanding of organometallic chemistry has led to new applications in research and industry - not least in relation to catalysis - and an extensive reaction schemes and structures give added clarity to the concepts being explained. Striking just the right balance between breadth and depth - and with features throughout to support the learning process - Organometallics and Catalysis is the perfect introduction for undergraduate and graduate students who need a thorough grounding on the subject or are embarking on new research areas. Online Resource Centre: The Online Resource Centre to accompany Organometallics and Catalysis: An Introduction features: For registered adopters of the text: - Figures from the book in electronic format For everyone: - Curated links to relevant video materials on YouTube
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. |
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