Topics in Organometallic Chemistry

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Latest release: January 6, 2024
Series
60
Books
Alkene Metathesis in Organic Synthesis
Book 1·Jul 2003
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Organometallic chemistry is a well established research area at the interface of organic and inorganic chemistry. In recent years this field has undergone a ren aissance as our understanding of organometallic structure, properties and mechanism has opened the way for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as medicine, biology, materials and polymer sciences and organic synthesis. For example, in the de velopment of new catalytic processes, organometallic chemistry is helping meet the challenge to society that the economic and environmental necessities of the future pose. As this field becomes increasingly interdisciplinary, we recognize the need for critical overviews of new developments that are of broad significance. This is our goal in starting this new series Topics in Organometallic Chemistry. The scope of coverage includes a broad range of topics of pure and applied or ganometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. Topics in Organometallic Chemistry differs from existing review series in that each volume is thematic, giving an overview of an area that has reached a stage of maturity such that coverage in a single review article is no longer possible. Furthermore, the treatment addresses a broad audience of researchers, who are not specialists in the field, starting at the graduate student level. Discussion of possible future research directions in the areas covered by the individual volumes is welcome.
Lanthanides: Chemistry and Use in Organic Synthesis
Book 2·Jul 2003
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With contributions by numerous experts
Activation of Unreactive Bonds and Organic Synthesis
Book 3·Jul 2003
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In the last few years a large repetoire of methods for the activation of unreactive organic functionalities and for their use in organic synthesis has been developed. In this volume, areas ranging from the activation of C-H bonds to the chemical transformation of dinitrogen are authoritatively discussed by leading experts in the field. To activate means to be able to cleave otherwise inert chemical bonds. The cleavage and formation of chemical bonds is fundamental to organic synthesis; these new activation methodologies make hitherto infeasible reactions extremely easy and create new opportunities for innovative organic transformations, for both industry and academia. This is the first book that provides a thorough and timely coverage of both inorganic and organic synthetic aspects of bond activation, thus giving a broad overview of the field and allowing both inorganic and organic chemists ready access to the methodologies involved.
Organometallic Bonding and Reactivity: Fundamental Studies
Book 4·Jul 2003
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The making and breaking of carbon-metal bonds is fundamental to all the processes of organometallic chemistry and metal mediated homogeneous or heterogeneous catalysis. The ever expanding scope of highly specific stoichiometric and catalytic transformations or organic substrates involving metals requires a thorough physical and theoretical understanding of fundamental principles of organometallic structure and reactivity. Diffraction experiments form the basis of tailoring the molecular architecture of organometallic compounds for specific functions. Mass spectrometric techniques possess the power to provide direct information on the energetics of transient species generated in the gas-phase. Computational chemistry with ab initio or density functional methods make a reliable numerical assessment of structures and (relative) energies increasingly feasible. Embedding methods, combining quantum chemistry with force field of semiempirical MO treatments, quantum dynamic studies and the computational modelling of solvent effects extend the utility of the basic methods. This volume in the series Topics in Organometallic Chemistry presents a survey by renowned experts of important experimental and theoretical developments to elucidate basic aspects of bonding, energetics, reaction mechanisms, molecular geometries and solid-state structures of organometallic compounds. Written by authors with frontier research expertise in their fields, both experimental and quantum chemical techniques, methodologies, results and interpretations are detailed in a manner suitable for the non-specialist, who seeks state-of-the-art information in the respective field.
Organolithiums in Enantioselective Synthesis
Book 5·Sep 2003
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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.
Transition Metal Arene π-Complexes in Organic Synthesis and Catalysis
Book 7·Sep 2004
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Metal-arene pi-complexes show a rich and varied chemistry. The metal adds a third dimension to the planar aromatic compounds and coordination of a metal to an arene thus not only altering the reactivity of ring-carbons and substituents but also makes possible reactions that lead to chiral non-racemic products. This book, organized in nine chapters and written by leading scientists in the field provides the reader with an up-to-date treatise on the subject organized according to reaction type and use. It covers the wide spectrum of arene activation: from the electrophilic activation of h6-bound arene by pi-Lewis acid metal complex fragments, to reactions of nucleophilic h2-coordinated arene complexes. The preparation of complexes is detailed, as are the scope, limitations and challenges of reactions in contemporary pi-arene metal chemistry with special attention given to asymmetric transformations. The emphasis of the book is on transformations of interest to organic synthesis and on the use of the complexes as catalysts or as chiral ligands.
The book is written for academic and industrial researchers in organic, organometallic, and inorganic chemistry as well as for advanced chemistry students.
Catalytic Carbonylation Reactions
Book 18·Sep 2006
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Carbonylation reactions are of major importance in both organic and industrial chemistry. Due to the availability, price and reactivity pattern, carbon monoxide is becoming a more and more important building block for fine and bulk chemicals. The major reaction types of carbon monoxide are comprehensively discussed by leading experts from academia and industry. The authors highlight important carbonylation reactions such as hydroformylation, alkoxy-carbonylations, co/olefin-copolymerization, Pauson-Khand reactions and others. They illustrate applications in organic synthesis and give industrial examples.
This volume is designed to provide graduate students and researchers with essential information on the use of carbon monoxide in organic synthesis. Therefore, the reader will get a balanced view of this developing and complex subject.
Dendrimer Catalysis
Book 20·Aug 2006
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Since the first application of dendrimers in catalysis in the mid 1990s, this field has advanced rapidly. As a consequence, catalytically active dendrimers have emerged as a class of molecular catalysts that has substantially enriched the field of homogeneous (and in part heterogeneous) catalysis. A general survey of transition metal dendrimer catalysts and the way they have developed is followed by in-depth discussions of dendritic transition metal catalysis based on non-covalent catalyst-support interaction and an overview of the rapidly growing field of stereoselective dendrimer catalysis. The development of dendrimer-encapsulated bimetallic nanoparticles has provided the interface with heterogeneous colloid catalysis. As cheaper and readily accessible alternatives to regular dendrimers, hyperbranched polymers are increasingly being used as catalyst platforms. These topics are complemented by a review of metallodendritic exoreptors for the redox recognition of oxo-anions and halides.
N-Heterocyclic Carbenes in Transition Metal Catalysis
Book 21·Feb 2007
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It was only in the early 1990s that carbenes with the carbene carbon being incorporated in a nitrogen containing heterocycle (N-heterocyclic carbenes or NHCs) were found to be stable enough to be isolated. Since the first report on the application of NHCs as ligands in transition metal catalysis in 1995, NHC have found numerous applications and have been established as a versatile and indispensable class of ligands. For many reactions like metathesis or cross-coupling reactions NHCs have often become the ligands of choice, allowing otherwise difficult transformations. In this book leading experts have surveyed major areas of application of NHC metal complexes in catalysis. The authors have placed a special focus on nickel- and palladium-catalyzed reactions, on applications in metathesis reactions, on oxidation reactions and on the use of chiral NHC-based catalysts. This compilation is rounded out by an introductory chapter and a chapter dealing with synthetic routes to NHC metal complexes. The use of NHC as ligands in catalysis has reached a certain level of maturity and this book allows the reader to get a balanced view of this increasingly important ligand class.
Organometallic Oxidation Catalysis
Book 22·Jan 2007
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Eighty per cent of all compounds produced in the chemical and pharmaceutical industries require at least one essential catalytic step during their synthesis. At the same time the use of hydrocarbons as a feed-stock for commodity and fine chemicals typically requires an oxidation step, which is usually mediated by a transition metal compound. Consequently oxidation catalysis is a major research field in chemistry, both in academia and in industry. In many such processes, species with metal-carbon bonds are formed as key intermediates, and these processes represent the primary focus of this volume. An important aspect covered by some of the expert contributors is the use of organic ligands - and thus organometallic complex metal fragments - to achieve efficient oxidation catalysis. It has not been self-evident that organometallic complexes can survive the conditions necessary for polar oxygen-transfer reactions, but research over the last decade concerning oxo and peroxo complexes functionalized by organic ligands has clearly shown that relatively non-polar M-C bonds can be quite stable in the presence of oxidants and protic media, and that they may even be essential for the favourable activity and life-time of a catalyst. Also considered in this context is the oxidation chemistry of basic organometallic species in the gas phase, as this may reveal fundamental characteristics inherent to oxidation catalysts.
Regulated Systems for Multiphase Catalysis
Book 23·Aug 2008
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Multiphase catalysis in recent years has been shown in academia and industry to be the emerging key technology for the competitive and sustainable production of fine chemicals in the next decades. It convincingly unites the indispensable core advantages of homogeneous catalysis with future governmental and industrial sustainability criteria. In a joint effort by seven of Germany's most distinguished scientists in the field and four renowned industry partners a research consortium was established which for the first time has systematically explored and related the main issues and mutual interdependencies of the different approaches in multiphase catalysis. This work has resulted in the development of an expert tool box, which relates the complex chemical and process based requirements to be considered when setting up a catalytic system. The resulting competence covers various fields as supercritical fluid (SCF) technology in catalysis, ionic liquids (Il), ligand design for SFCs and Ils, thermomorphic solvent systems, reactor design and many more. The reader will receive a critical survey of the state of the art together with suggestions helping to choose on which integrated catalyst/solvent/condition-system is probably best for a given transformation.
Directed Metallation
Book 24·Oct 2007
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Directed metalation is recognized as one of the most useful methodologies for the regio- and stereoselective generation of organometallic species, the generation of which necessarily leads to the selective formation of organic products. Cyclometalation using Li, Mn, and Pd, and directed hydrometalation and carbometalation using Al and Zn, have been utilized for regio- and/or stereoselective synthesis for decades. Recently, a new chelation-assisted methodology has been developed not only for controlling regio- and stereoselectivity of reactions, but also for accelerating reactions. In particular, chelation-methodology has been utilized as a new activation method, in which a carbon-metal bond is generated directly from a C-H bond; a reaction rarely achieved using conventional methods. A wide variety of catalytic functionalization reactions of C-H bonds by the utilization of a chelation, have been developed recently and are comprehensively discussed in this book by leading experts. In addition, new approaches to directed hydrometalation and directed carbometalation as a key step are also discussed. A unique stereo- and regioselective hydroformylation has been developed through the utilization of directed hydrometalation. The regioselective Mizoroki-Heck reaction is another example in which directed carbometalation can be used to achieve a high regioselectivity. These examples emphasize how these innovative methodologies are contributing to different fields of chemistry.
Bio-inspired Catalysts
Book 25·Feb 2009
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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.
Metal Catalysts in Olefin Polymerization
Book 26·Feb 2009
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Polyolefin is a major industry that is important for our economy and impacts every aspect of our lives. The discovery of new transition metal-based catalysts is one of the driving forces for the further advancement of this field. Whereas the classical heterogeneous Ziegler-Natta catalysts and homogeneous early transition metal metallocene catalysts remain the workhorses of the polyolefin industry, in roughly the last decade, tremendous progress has been made in developing non-metallocene-based olefin polymerization catalysts. Particularly, the discovery of late transition metal-based olefin polymerization catalysts heralds a new era for this field. These late transition metal complexes not only exhibit high activities rivaling their early metal counterparts, but more importantly they offer unique properties for polymer architectural control and copolymerization with polar olefins. In this book, the most recent major breakthroughs in the development of new olefin polymerization catalysts, including early metal metallocene and non-metallocene complexes and late transition metal complexes, are discussed by leading experts. The authors highlight the most important discoveries in catalysts and their applications in designing new polyolefin-based functional materials.
Conducting and Magnetic Organometallic Molecular Materials
Book 27·Jun 2009
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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.
Molecular Organometallic Materials for Optics
Book 28·Oct 2009
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S. Di Bella, C. Dragonetti, M. Pizzotti, D. Roberto, F. Tessore, R. Ugo: Coordination and Organometallic Complexes as Second-Order Nonlinear Optical Molecular Materials.- M. G. Humphrey, M.P. Cifuentes, M. Samoc: NLO Molecules and Materials Based on Organometallics: Cubic NLO Properties.- L. Murphy, J. A. G. Williams: Luminescent Platinum Compounds: From Molecules to OLEDs. - Z. Liu, Z. Bian, C. Huang: Luminescent Iridium Complexes and Their Applications.- N. C. Fletcher, M. C. Lagunas: Chromo- and Fluorogenic Organometallic Sensors.- V. Guerchais, H. Le Bozec: Metal Complexes Featuring Photochromic Ligands.
Photophysics of Organometallics
Book 29·Dec 2009
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Arvind Kumar, Shih-Sheng Sun, and Alistair J. Lees: Photophysics and Photochemistry of Organometallic Rhenium Diimine Complexes; Conor Long: Photophysics of CO Loss from Simple Metal Carbonyl Complexes; Antonín Vlcek Jr: Ultrafast Excited-State Processes in Re(I) Carbonyl-Diimine Complexes: From Excitation to Photochemistry; Kenneth Kam-Wing Lo: Exploitation of Luminescent Organometallic Rhenium(I) and Iridium(III) Complexes in Biological Studies; Maria L. Muro , Aaron A. Rachford , Xianghuai Wang, and Felix N. Castellano: Platinum II Acetylide Photophysics; Andreas F. Rausch, Herbert H. H. Homeier, and Hartmut Yersin: Organometallic Pt(II) and Ir(III) Triplet Emitters for OLED Applications and the Role of Spin–Orbit Coupling: A Study Based on High-Resolution Optical Spectroscopy.
Transition Metal Complexes of Neutral eta1-Carbon Ligands
Book 30·Dec 2009
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Contents: Yves Canac and Remi Chauvin: Neutral eta1-carbon ligands: beyond carbon monoxide; Esteban P. Urriolabeitia: Ylide Ligands; Wolfgang Petz and Gernot Frenking: Carbodiphosphoranes and related ligands; Mareike C. Jahnke and F. Ekkehardt Hahn: Chemistry of N-Heterocyclic Carbene Ligands; Tsuyoshi Kato, Eddy Maerten, Antoine Baceiredo: Non-NHCs stable singlet carbene ligands; Victorio Cadierno, Sergio E. García-Garrido: All-Carbon-Substituted Allenylidene and Related Cumulenylidene Ligands; Victorio Cadierno, Sergio E. García-Garrido: Heteroatom-Conjugated Allenylidene and Related Cumulenylidene Ligands.
C-X Bond Formation
Book 31·Jun 2010
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Contents: Kilian Muñiz: Transition Metal Catalyzed Electrophilic Halogenation of C-H bonds in alpha-Position to Carbonyl Groups; Arkadi Vigalok * and Ariela W Kaspi: Late Transition Metal-Mediated Formation of Carbon-Halogen Bonds; Paul Bichler and Jennifer A. Love*: Organometallic Approaches to Carbon-Sulfur Bond Formation; David S. Glueck: Recent Advances in Metal-Catalyzed C-P Bond Formation; Andrei N. Vedernikov: C-O Reductive Elimination from High Valent Pt and Pd Centers; Lukas Hintermann: Recent Developments in Metal-Catalyzed Additions of Oxygen Nucleophiles to Alkenes and Alkynes; Moris S. Eisen: Catalytic C-N, C-O and C-S bond formation promoted by organoactinide complexes.
Medicinal Organometallic Chemistry
Book 32·Sep 2010
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Contents: Gérard Jaouen, Nils Metzler-Nolte : Introduction ; Stéphane GIBAUD and Gérard JAOUEN: Arsenic - based drugs: from Fowler’s solution to modern anticancer chemotherapy; Ana M. Pizarro, Abraha Habtemariam and Peter J. Sadler : Activation Mechanisms for Organometallic Anticancer Complexes; Angela Casini, Christian G. Hartinger, Alexey A. Nazarov, Paul J. Dyson : Organometallic antitumour agents with alternative modes of action; Elizabeth A. Hillard, Anne Vessières, Gerard Jaouen : Ferrocene functionalized endocrine modulators for the treatment of cancer; Megan Hogan and Matthias Tacke : Titanocenes – Cytotoxic and Anti-Angiogenic Chemotherapy Against Advanced Renal-Cell Cancer; Seann P. Mulcahy and Eric Meggers : Organometallics as Structural Scaffolds for Enzyme Inhibitor Design; Christophe Biot and Daniel Dive : Bioorganometallic Chemistry and Malaria; Nils Metzler-Nolte : Biomedical applications of organometal-peptide conjugates; Roger Alberto : Organometallic Radiopharmaceuticals; Brian E. Mann : Carbon Monoxide – an essential signaling molecule.