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A succinct review of the essential concepts of organometallic chemistry, 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.
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.
This volume presents the latest developments in the use of organometallic catalysis for the formation of bulk chemicals and the production of energy, via green processes including efficient utilization of waste feedstocks from industry. The chemistry of carbon dioxide relating to its hydrogenation into methanol –an eco-friendly energy storage strategy– and its uses as C1 synthon for the formation of important building-blocks for fine chemicals industry are covered. Catalytic hydrogenations of various functional groups and hydrogen transfer reactions including the use of first row metal catalysts are presented as well as the conversion of alcohols to carboxylates via hydrogen transfer with a zero-waste strategy using water. Transformation of renewable or bio-based raw materials is surveyed through alkene metathesis and C–O bond activations and functionalizations. A green aspect for selective formation of C-C, C-O and C-N bonds involves direct regioselective C–H bond activations and functionalizations. These transformations can now be promoted under mild reaction conditions due to the use photoredox catalyts. C–H bond oxidation using visible light leads mainly to the formation of C–O and C–N bonds, whereas cross-coupled C–C bonds can be formed through the radical additions on (hetero) arenes using photoredox assisted mechanism.
Vor allem an Studenten fortgeschrittener Semester und Doktoranden gerichtet ist dieses Lehrbuch der Katalyse mit metallorganischen Verbindungen, das auch biologisch relevanten Reaktionen viel Platz einräumt. Hervorragend zum Selbststudium geeignet - mit zahlreichen Übungsaufgaben, nach Schwierigkeitsgraden geordnet und durch Lösungen ergänzt.
Organometallic Mechanisms and Catalysis: The Role of Reactive Intermediates in Organic Processes covers the mechanistic delineation of organometallic chemistry and catalysis. This book is organized into three parts encompassing 18 chapters. The first part describes first the oxidation-reduction process of organometals, followed by discussions on the catalytic reactions of peroxides, metal-catalyzed addition to olefins, and reduction of organic halides. This part also explores other reactions involving transition metal carbonyls and metal-catalyzed reactions of aromatic diazonium salts. The second part deals with some chemical aspects of organometals, such as their stability, thermochemistry, decomposition, hemolytic pathways, and the formation of carbon-carbon bonds. The third part examines the charge transfer processes and interactions of organometals with electron acceptors. This part further looks into the cleavage and insertion reactions of organometals with electrophiles, as well as the electrophilic and electron transfer mechanisms of organometals. Organic and inorganic chemists, teachers, and students will greatly benefit from this book.
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, Benoît 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.
From the beginning of chemistry as an exact (natural) science - almost 200 years ago - there was a more or less distinct differentiation between its various branches such as organic, inorganic, physical, analytical, or biochemistry. With the increasing insight into the connections and governing laws it soon became obvious, however, that such a clear separation could be regarded as more or less obsolete; within almost any field of chemical research one has to deal with most of the branches mentioned. Especially organic and inorganic chemistry are significant examples for this statement, overlapping considerably within the important field of organome tallic chemistry. This regime of chemistry started its advance with the discovery of dimethylzinc 150 years ago, had a highlight with the introduction of Grignard reagents around 1900, developed further with the start of lithium organyls in 1925 and literally exploded after the discovery of the first transition metal cyclopenta dienyl complex ferrocene half a century ago. The chronological sequence of the important steps, i. e. 1850 (Zn) - 1900 (Mg) - 1925 (Li) - 1950 (Fe), seems rather remarkable. The increasing group of metallocenes is not only of high theoretical and, due to the potential chirality of its members, stereochemical interest, but offers also a wide variety of extremely useful catalysts, especially for stereoselective reactions. The Austrian Chemical Society took this development into account by organizing the Twelfth International Conference on Organometallic Chemistry held in Vienna in 1985.
More than 30 years after the discovery of transition metals and organometal lics as catalysts for olefin polymerization these catalysts did not have lost their fascination. Since 1953 when Karl Ziegler has discovered the catalytic polymerization of ethylene leading to plastically formable polymers which are mechanically stable up to temperatures of about 100°C, synthetic polymers and rubbers have made their way right into private houses. This discovery has been a main impetus for the fast growing production of plastics. The stereoselective poly merization of propylene and other long-chain a-olefins first detected by Giulio Natta leads to an even broadened field of applications. Another enforcing factor were the developments of Standard Oil of Indiana and Phillipps Petroleum Company who engaged in the polymerization of a-olefins supported molybdenum, cobalt and later on chromium catalysts which clearly indicates the wide variety of suitable systems. This kind of research acknowledged merit when in 1963 the Nobel prize of chemistry was awarded to Ziegler and Natta. Although to a great extent there is a technical application for these catalysts, up to now the nature of the active centres and many reaction mechanisms are not completely known.
Over the past 20 years aqueous organometallic catalysis has found applications in small- scale organic synthesis in the laboratory, as well as in the industrial production of chemicals with a combined output close to one million tons per year. Aqueous/organic two-phase reactions allow easy product-catalyst separation and full catalyst recovery which mean clear benefits not only in economic but also in environmental and green chemistry contexts. Instead of putting together a series of expert reviews of specialized fields, this book attempts to give a comprehensive yet comprehensible description of the various catalytic transformations in aqueous systems as seen by an author who has been working on aqueous organometallic catalysis since its origin. Emphasis is put on the discussion of differences between related non-aqueous and aqueous processes due to the presence of water. The book will be of interest to experts and students working in catalysis, inorganic chemistry or organic synthesis, and may serve as a basis for advanced courses.
Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book. The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper understanding of the underlying reaction mechanism and correlation between molecular structure and reactivity. The contributions represent a wealth of first-hand information from renowned experts working in these disciplines, covering such topics as activation of small molecules, C-C and C-Heteroatom bonds formation, cross-coupling reactions, carbon dioxide converison, homogeneous and heterogeneous transition metal catalysis and metal-graphene systems. With the knowledge gained, the reader will be able to improve existing reaction protocols and rationally design more efficient catalysts or selective reactions. An indispensable source of information for synthetic, analytical, and theoretical chemists in academia and industry.