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Books > Science & Mathematics > Chemistry > Organic chemistry > Organometallic chemistry
This thesis describes the synthesis and characterization of numerous metal-metal bonded complexes that are stabilized by extremely bulky amide ligands. It provides a comprehensive overview of the field, including discussions on groundbreaking complexes and reactions, before presenting in detail, exciting new findings from the PhD studies. The thesis appeals to researchers, professors and chemistry undergraduates with an interest in inorganic and/or organometallic chemistry.
The study of clusters is one of the most exciting topics in the rapidly developing field of nanostructured materials. As discussed in this book, nanometer-sized metal particles can be obtained not only by evaporation methods, producing atomic or molecular beams, but also by the chemical synthesis of metal cluster compounds. These have a well-defined stoichiometry and are composed of metal clusters of a given, homogeneous size, each cluster being surrounded by a shell of ligand molecules. Accordingly, the compounds provide excellent model systems for macroscopic assemblies of small metal particles embedded in a dielectric solid. The underlying physical properties are described in terms of a three-dimensional matrix of mutually separated quantum wells. In going from one compound to another, the size and separation of the quantum wells may be varied. In this way, one may study such fundamental properties as the size-induced transition from metallic to molecular behaviour. At the same time, the electronic level structure may be changed in a controlled way, which should confer tunable optical, electrical or magnetic properties.
Spectroscopic Properties of Inorganic and Organometallic Compounds provides a unique source of information on an important area of chemistry. Divided into sections mainly according to the particular spectroscopic technique used, coverage in each volume includes: NMR (with reference to stereochemistry, dynamic systems, paramagnetic complexes, solid state NMR and Groups 13-18); nuclear quadrupole resonance spectroscopy; vibrational spectroscopy of main group and transition element compounds and coordinated ligands; and electron diffraction. Reflecting the growing volume of published work in this field, researchers will find this Specialist Periodical Report an invaluable source of information on current methods and applications. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading experts in their specialist fields, this series is designed to help the chemistry community keep current with the latest developments in their field. Each volume in the series is published either annually or biennially and is a superb reference point for researchers. www.rsc.org/spr
This book presents Pd- and Ni-catalyzed transformations generating functionalized heterocycles. Transition metal catalysis is at the forefront of synthetic organic chemistry since it offers new and powerful methods to forge carbon-carbon bonds in high atom- and step-economy. In Chapter 1, the author describes a Pd- and Ni-catalyzed cycloisomerization of aryl iodides to alkyl iodides, known as carboiodination. In the context of the Pd-catalyzed variant, the chapter explores the production of enantioenriched carboxamides through diastereoselective Pd-catalyzed carboiodination. It then discusses Ni-catalyzed reactions to generate oxindoles and an enantioselective variant employing a dual ligand system. Chapter 2 introduces readers to a Pd-catalyzed diastereoselective anion-capture cascade. It also examines diastereoselective Pd-catalyzed aryl cyanation to synthesize alkyl nitriles, a method that generates high yields of borylated chromans as a single diastereomer, and highlights its synthetic utility. Lastly, Chapter 3 presents a Pd-catalyzed domino process harnessing carbopalladation, C-H activation and -system insertion (benzynes and alkynes) to generate spirocycles. It also describes the mechanistic studies performed on these reactions.
In many of the processes of oxidation catalysis, 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 contributors is the use of organic ligands to achieve efficient oxidation catalysis. Each volume of "Topics in Organometallic Chemistry" provides a comprehensive summary and critical overview of a specific topic in organometallic chemistry.
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.
This book describes novel synthetic methodologies for two kinds of structurally elaborate metal complexes: a heterometallic complex and a tetrahedral chiral-at-metal complex. The book provides the tools and inspiration to chemists for development of metal complexes with wide structural diversity than had previously been possible. For each of the two topics, existing synthetic methods for similar compounds are discussed first, and then new strategies are presented, followed by the demonstration of the synthesis of novel compounds supported by experimental results. Both of the final products in this research, a Co-Ni heterometallic complex covered in the first topic and a tetrahedral chiral-at-metal complex in the second one are difficult to obtain by using common synthetic methods for thermodynamic reasons. This research achieved highly selective syntheses of these compounds using newly designed strategies that enable precise kinetic control. Such an approach will be useful for synthesizing other new metal complexes. Since the last century, organic chemistry has flourished with the development of a variety of synthetic techniques that make precise kinetic control possible. Coordination chemistry of 3d or main-group transition metals has been mainly based on simple one-step reactions that yield only thermodynamic products. The publication of this book helps pave the way to kinetically controlled precise syntheses of various metal complexes.
Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.
This book presents an advanced state-of-the-art report on the Fischer and Schrock type carbyne complexes and demonstrates their wide application to organic and organometallic synthesis, as well as their considerable role in metathesis. Most of the articles are written by leading researchers in this field, describing their fascinating research in their own words. This carbyne book discusses in detail the breadth and diversity of metal-carbon multiple bond chemistry of different d and f-block elements. Besides theoretical, structural, photochemical and electrochemical studies, this volume provides a fascinating introduction to heterometallic carbon-bridged compounds to conjugated complexes and polymers derived from metal-carbyne building blocks. An extensive part of this book discusses aspects of olefin metathesis, metal-induced addition, cycloaddition and carbon-carbon coupling reactions by well-characterized carbene and carbyne complexes. (abstract) This book presents an advanced state-of-the-art report on the Fischer and Schrock type carbyne complexes, discussing specific aspects of the metal carbon multiple bond chemistry of different d and f-block elements, such as synthetic, theoretical, structural, photochemical and electrochemical studies. Special chapters focus on catalysis and olefin metathesis as well as metal induced addition, cycloaddition and carbon-carbon coupling reactions.
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 third edition retains the general level and scope of earlier editions, but has been substantially updated with over 900 new references covering the literature through 2005, and 140 more pages of text than the previous edition. In addition to the general updating of materials, there is new or greatly expanded coverage of topics such as Curtin-Hammett conditions, pressure effects, metal hydrides and asymmetric hydrogenation catalysts, the inverted electron-transfer region, intervalence electron transfer, photochemistry of metal carbonyls, methyl transferase and nitric oxide synthase. The new chapter on heterogeneous systems introduces the basic background to this industrially important area. The emphasis is on inorganic examples of gas/liquid and gas/liquid/solid systems and methods of determining heterogeneity.
This book presents several helpful synthetic methods for diverse multinuclear complexes. The results described can be used to selectively connect mononuclear as well as multinuclear complexes with other metal complexes to construct valuable photofunctional compounds. Using the new synthetic methods, it was possible to selectively connect several types of metal complexes in a single step under relatively mild reaction conditions. This so-called building block approach utilizes various C-C coupling reactions between metal complexes with functional groups as active moieties. Owing to the large pi-conjugation systems, the multinuclear complexes synthesized using coupling reactions showed a strong absorption ability over a wide range of visible light and long emission lifetimes, which are ideal properties for photosensitizers and light absorbers. By combining these coupling methods with the newly developed hydrogenation reactions, the binding mode of the linkers in multinuclear complexes can be modified in order to tune the photophysical properties and photocatalytic ability. As such, the synthesized multinuclear complexes can be used for various purposes, e.g., as photocatalysts and photosensitizers, and in light-harvesting systems. The synthetic methods and strategies presented in this book diversify not only the structures but also functions of multinuclear complexes.
This edited volume focuses on the host-guest chemistry of organic molecules and inorganic systems during synthesis (structure-direction). Organic molecules have been used for many years in the synthesis of zeolitic nanoporous frameworks. The addition of these organic molecules to the zeolite synthesis mixtures provokes a particular ordering of the inorganic units around them that directs the crystallization pathway towards a particular framework type; hence they are called structure-directing agents. Their use has allowed the discovery of an extremely large number of new zeolite frameworks and compositions. This volume covers the main aspects of the use of organic molecules as structure-directing agents for the synthesis of zeolites, including first an introduction of the main concepts, then two chapters covering state-of-the-art techniques currently used to understand the structure-directing phenomenon (location of molecules by XRD and molecular modeling techniques). The most recent trends in the types of organic molecules used as structure-directing agents are also presented, including the use of metal-complexes, the use of non-ammonium-based molecules (mainly phosphorus-based compounds) and the role of supramolecular chemistry in designing new large organic structure-directing agents produced by self-aggregation. In addition the volume explores the latest research attempting to transfer the asymmetric nature of organic chiral molecules used as structure-directing agents to the zeolite lattice to produce chiral enantioselective frameworks, one of the biggest challenges today in materials chemistry. This volume has interdisciplinary appeal and will engage scholars from the zeolite community with a general interest in microporous materials, which involves not only zeolite scientists, but also researchers working on metal-organic framework materials. The concepts covered will also be of interest for researchers working on the application of materials after encapsulation of molecules of interest in post-synthetic treatments. Further the work explores the main aspects of host-guest chemistry in hybrid organo-inorganic templated materials, which covers all types of materials where organic molecules are used as templates and are confined within framework-structured inorganic materials (intercalation compounds). Therefore the volume is also relevant to the wider materials chemistry community.
Advances in Organometallic Chemistry, Volume 72, contains authoritative review articles of worldwide researchers in organometallic chemistry. This longstanding serial is known for its comprehensive coverage of topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more. Chapters in this updated release include Propargylidyne and Tricarbido Complexes, Metal carbonyl promoted multicomponent coupling of alkyne for synthesis of heterocyclic compounds, Group 10 metal(0) complexes stabilized by phosphorus and carbon donor ligands, Recent advances in gold catalyzed cycloadditions or Annulations of alkynes to access heterocyclic compounds, and Ion pairing and in situ ligand modification effects on the reactivity of molecular catalysts for olefin polymerization.
This volume gives an overview of the applications of organometallic chemistry in process chemistry relevant to the current topics in synthetic chemistry. This volume starts with an introduction on the historical development of organometallics in process chemistry and is followed by chapters dealing with the last five years' development in various organometallic reaction types such as the challenging cross coupling process, construction of 3.1.0 bicycles, pressure and transfer hydrogenations of historically challenging compounds such as esters, utilization of carbon dioxide for making organic compounds by flow process, drug synthesis and metal detection and scavenging in the finished APIs. A chapter by Colacot et.al., is also devoted to the process development and structural understanding of organometallic catalysts with particular emphasis to LnPd(0) catalysts. An academia - industry collaborated chapter on the use of water as a solvent for organometallic processes is included in this book.
This book highlights and investigates novel solid-state luminescent properties of crystals with stimuli-responsive behavior. Several novel molecular designs for controlling crystal structures with photo-physical properties are described, with a special focus on external stimuli-responsive properties. The major goal of the material design concept was to capitalize on the chirality of crystals with stimuli-responsive properties. To allow crystals' chirality to be controlled and modified by means of external stimulation, the axial chirality of biaryl moiety was employed and, interestingly, produced several novel mechano- and vapo-responsive luminescent properties based on crystal-to-crystal or single-crystal-to-single-crystal phase transitions. In addition, the book details how the molecular rotation of luminophores in the solid phase can be used to achieve corresponding thermal-responsive phosphorescence. The reports presented here illustrate how the author has succeeded in controlling structural factors in a bulk environment by using molecular design with linking to photo-physical properties. The content will be of great interest to researchers in the field, and to members of chemical and material science societies.
Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.
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.
Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.
Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.
About eight years ago, the catalytic carbonylation of organic nitro compounds was a research field developed enough to justify a rather long review on this subject. Now, we feel that the scientific results and new achievements in this field, very important even from an industrial point of view, require a book in order to be adequately presented. The competition between the catalytic carbonylation of organic nitro compounds and other chemical routes for the synthesis of a variety of organic compounds has not yet come to an end, but many progresses have been done in the former field. We also like to emphasize that this type of research does not only involve relevant industrial problems to be solved, but it opens a research field where the academic interests (mechanism of the reactions, isolation of the intermediates in the catalytic cycles, synthesis of model compounds and so on) can find a lot of opportunities.
The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. 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.The chapter "Enamine/Transition Metal Combined Catalysis: Catalytic Transformations Involving Organometallic Electrophilic Intermediates" is available open access under a CC BY 4.0 License via link.springer.com.
The demand for novel efficient and environmentally sustainable chemo, regio- and stereoselective catalyst systems for the oxidation of organic substrates is continuously growing in line with toughening economic and environmental constraints. This book addresses these issues; it consists of eleven chapters written by world-recognized experts in green and sustainable oxidation catalysis. The most urgent and challenging topics, in the judgment of the editor, such as green asymmetric epoxidations, sulfoxidatiuons, C-H oxidations; oxidation catalysis by polyoxometalates and oxidations in non-conventional solvents, etc. have been critically reviewed in this book. Both fundamental aspects, such as catalysts design, catalytic properties, nature of catalytically active sites and reaction mechanisms, and practical outlook of the oxidations have been addressed by the authors. The book appeals to a broad readership, particularly graduate students, employees of universities and research organizations, and industrial researchers, particularly those working in the areas of homogeneous oxidation catalysis, asymmetric synthesis, organocatalysis, sustainable catalytic processes and green chemistry, mechanisms of catalytic reactions, synthesis of bioactive compounds, biomimetic chemistry, etc. Konstantin Bryliakov is Leading Researcher at the Boreskov Institute of Catalysis. In 2016, he was elected Honorary Professor of the Russian Academy of Sciences.
Homogeneous catalysis plays an important role both in the laboratory and in the industry. Successful applications in industry involve new polymerisation processes with complexes of zirconium and related metals, new carbonylation processes employing palladium and rhodium, ring opening polymerisations, and new enantioselective isomerisation catalysts as in the preparation of menthol. Also in the synthesis of organic compounds in the laboratory highly selective homogeneous catalysts represent an irreplaceable part of the toolbox of the synthetic chemist. Examples of such reactions are cross-coupling (Ni, Pd), nucleophilic substitution of allylpalladium complexes, Heck reactions (Pd), asymmetric epoxidation, Wacker type reactions (Pd), asymmetric hydrogenations (Rh, Ru), reactions of chromium complexes, enantioselective reactions with Lewis acids, reactions with the McMurry reagent, etc. There is hardly any multistep organic synthesis that does not involve one of these metal catalysed reactions. Most of these catalysts have been developed by empiricism. The metal catalysed processes consist of a series of elementary steps which often have been studied in isolation in organometallic chemistry. The knowl- edge of such elementary steps - effect ofligands, anions, coordination number, valence states - has greatly contributed to the development of improved cata- lysts for the reactions mentioned above. In addition to the empirical approach theoretical methods have given support and guidance to the development of improved processes. Often the key steps of a cycle escape from a direct ob- servation and then theoretical contributions are even more wanted.
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