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This book provides researchers in the fields of organic chemistry, organometallic chemistry and homogeneous catalysis with an overview of significant recent developments in the area of metal-ligand cooperativity, with a focus on pincer architectures. The various contributions highlight the widespread impact of M–L co-operativity phenomena on modern organometallic chemistry and catalyst development. The development of efficient and selective catalytic transformations relies on the understanding and fine control of the various elementary reactions that constitutes a catalytic cycle. Co-operative ligands, which actively participate in bond making and bond breaking together to the metal they support, open up new avenues in this area. In particular, buttressing a weak or reactive metal-ligand bond by flanking coordinating arms in a pincer ligand design is proving a versatile strategy to access robust metal complexes that exhibit unusual and selective reactivity patterns.

Introduces an innovative and outstanding tool for the easy synthesis of complex chiral structures in a single step Covering all of the literature since the beginning of 2006, this must-have book for chemists collects the major progress in the field of enantioselective one-, two-, and multicomponent domino reactions promoted by chiral metal catalysts. It clearly illustrates how enantioselective metal-catalyzed processes constitute outstanding tools for the development of a wide variety of fascinating one-pot asymmetric domino reactions, thereby allowing many complex products to be easily generated from simple materials in one step. The book also strictly follows the definition of domino reactions by Tietze as single-, two-, as well as multicomponent transformations. Asymmetric Metal Catalysis in Enantioselective Domino Reactions is divided into twelve chapters, dealing with enantioselective copper-, palladium-, rhodium-, scandium-, silver-, nickel-, gold-, magnesium-, cobalt-, zinc-, yttrium and ytterbium-, and other metal-catalyzed domino reactions. Most of the chapters are divided into two parts dealing successively with one- and two-component domino reactions, and three-component processes. Each part is subdivided according to the nature of domino reactions. Each chapter of the book includes selected applications of synthetic methodologies to prepare natural and biologically active products. -Presents the novel combination of asymmetric metal catalysis with the concept of fascinating domino reactions, which allows high molecular complexity with a remarkable level of enantioselectivity -Showcases an incredible tool synthesizing complex and diverse chiral structures in a single reaction step -Includes applications in total synthesis of natural products and biologically active compounds -Written by a renowned international specialist in the field -Stimulates the design of novel asymmetric domino reactions and their use in the synthesis of natural products, pharmaceuticals, agrochemicals, and materials Asymmetric Metal Catalysis in Enantioselective Domino Reactions will be of high interest to synthetic, organic, medicinal, and catalytic chemists in academia and R&D departments.

In this thesis, the author outlines the construction of active structure and modulation of catalytic reactivity of Pt-based bi-component catalysts, from the model systems to real supported catalysts. The thesis investigates the promotion effect of the second components on catalytic performance of Pt catalysts, and presents the reversible generation of the “sandwich-like” structure of Pt-Ni catalysts, containing both surface NiO1-X and subsurface Ni by alternating redox treatments at medium temperature. With the aid of single layer graphene, the dynamic process of chemical reactions occurring on the Pt(111) surface can be visualized using in-situ LEEM and DUV-PEEM techniques, the results of which are included here. The author reveals that the graphene layer exhibits a strong confinement effect on the chemistry of molecules underneath and the intercalated CO can desorb from the Pt surface around room temperature and in UHV, which may promote the CO oxidation confined under graphene.

The second edition of the Handbook of Metathesis, edited by Nobel Prize Winner Robert H. Grubbs and his team, is available as a 3 Volume set as well as individual volumes. Volume 1, edited by R. H. Grubbs together with A. G. Wenzel focusses on Catalyst Development and Mechanism. The new edition of this set is completely updated (more than 80% new content) and expanded, with a special focus on industrial applications. Written by the'Who-is-Who'of metathesis, this book gives a comprehensiveand high-quality overview. It is the perfect and ultimate one-stop-reference source in this field and indispensable for chemists in academia and industry alike.View the set here - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527334246.html Other available volumes: Volume 2: Applications in Organic Synthesis, Editors: R. H. Grubbs and D. J. O´Leary - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339493.html Volume 3: Polymer Synthesis, Editors: R. H. Grubbs and E. Khosravi - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339507.html

The oxidation of primary and secondary alcohols to the corresponding carbonyl compounds is of fundamental importance in organic synthesis, due to the wide use of these products as precursors and intermediates for many drugs, vitamins and fragrances. However, traditional oxidants are often toxic and release considerable amounts of by-products. As an alternative, oxygen is among the cheaper and less polluting stoichiometric oxidants, and the implementation of a transition metal-based catalyst in combination with oxygen represents an emerging alternative to the traditional procedures. This book aims to give an overview of the aerobic oxidation of alcohols catalyzed by transition metals, and covers the most important advances in the last fifteen years. Following an introductory chapter on homogeneous-, heterogeneous- and nano-catalysis, use of copper, ruthenium, palladium, gold, vanadium and iron are discussed in turn. The book concludes with a useful overview that includes representative experimental procedures. This book will provide a valuable reference to organic chemists and green chemists in academia and industry.

Antoine Simonneau's thesis highlights the development of new cycloisomerization reactions through the activation of alkynes with gold complexes. First Simonneau describes 1,6-enynes and their direct conversion into allenes through 1,5-hydride or ester migration processes. The author and his team used appropriate propargylic functional groups to achieve this conversion. This study shows that O-tethered 1,6-enynes carrying a strained cycloalkane at the propargylic position could undergo a cyclopropanation/ring expansion cascade reaction. The author employed this rearrangement as the starting point in the design of a new macro cycle synthesis. The next part of the thesis focuses on the cycloisomerization of diynes involving as the first step of the process the rearrangement of one alkyne partner into an allene thanks to a gold-catalyzed 1,3-shift of a propargylic ester. The thesis discloses a new cycloisomerization pattern featuring a 1,5-carbonyl transfer, giving rise to unprecedented cross-conjugated diketones. In the final part of the research, Simmoneau investigates the gold-catalyzed cycloisomerization mechanism of 1,6-enynes and questions the intermediacy of gold acetylides. By the means of NMR and mass spectrometry analysis, theoretical treatment and solution experiments, it was possible to rule out the involvement of these species in the catalytic cycle. This thesis has led to a number of publications in high-impact journals.

The book describes the valorization of biomass-derived compounds over gold catalysts. Since biomass is a rich renewable feedstock for diverse platform molecules, including those currently derived from petroleum, the interest in various transformation routes has become intense. Catalytic conversion of biomass is one of the main approaches to improving the economic viability of biorefineries. In addition, Gold catalysts were found to have outstanding activity and selectivity in many key reactions. This book collects information about transformations of the most promising and important compounds derived from cellulose, hemicelluloses, and woody biomass extractives. Since gold catalysts possess high stability under oxidative conditions, selective oxidation reactions were discussed more thoroughly than other critical reactions such as partial hydrogenation, acetalization, and isomerization. The influence of reaction conditions, the role of the catalyst, and the advantages and disadvantages of using gold are presented for all of the reactions mentioned above. This book provides an overview of the recent research results focusing on application of gold catalysts for synthesis of valuable chemicals using renewable feedstocks.

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.

It is now IS years since the first patents in polymer supported metal complex catalysts were taken out. In the early days ion-exchange resins were used to support ionic metal complexes. Soon covalent links were developed, and after an initially slow start there was a period of explosive growth in the mid to late 1970s during which virtually every homogeneous metal complex catalyst ever reported was also studied bound to a support. Both polymers and inorganic oxides were studied as supports, although the great preponderance of workers studied polymeric supports, and of these polystyrene was by far the commonest used. This period served to show that by very careful design polymer-supported metal complex catalysts could have specific advantages over homogeneous metal complex catalysts. However the subject was a complicated one. Merely immobilising a successful metal complex catalyst to a functionalised support rarely yielded other than an inferior version of the catalyst. Amongst the many discouraging results of the 1970s, there were more than enough results that were sufficiently encouraging to demonstrate that, by careful design, supported metal complex catalysts could be prepared in which both the metal complex and the support combined together to produce an active catalyst which, due to the combination of support and complex, had advantages of activity, selectivity and specificity not found in homogeneous catalysts. Thus a new generation of catalysts was being developed.

Homogeneous catalysis by soluble metal complexes has gained considerable attention due to its unique applications and features such as high activity and selectivity. Catalysis of this type has demonstrated impressive achievements in synthetic organic chemistry and commercial chemical technology. Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms presents a comprehensive summary of the results obtained over the last sixty years in the field of the kinetics and mechanisms of organic and inorganic reactions catalyzed with metal complexes. Topics covered include: Specific features of catalytic reaction kinetics in the presence of various mono- and polynuclear metal complexes and nanoclusters Multi-route mechanisms and the methods of their identification, as well as approaches to the kinetics of polyfunctional catalytic systems Principles and features of the dynamic behavior of nonlinear kinetic models The potential, achievements, and limitations of applying the kinetic approach to the identification of complex reaction mechanisms The development of a rational strategy for designing kinetic models The kinetic models and mechanisms of many homogeneous catalytic processes employed in synthetic and commercial chemistry Written for specialists in the field of kinetics and catalysis, this book is also relevant for post-graduates engaged in the study

Over the past decade, much research effort has been devoted to the design and synthesis of new reagents and catalysts that can influence carbon-hydrogen bond activation, mainly because of the prospect that C−H activation could enable the conversion of cheap and abundant alkanes into valuable functionalized organic compounds. Alkane C-H Activation by Single-Site Metal Catalysis presents the current state-of-the-art development in the catalytic systems for the catalytic trans-formations of alkanes under homogeneous conditions. Chapter 1 offers a comprehensive summary of the main discoveries realized so far. Chapter 2 reviews the so-called electrophilic activation, initiated by Shulpín in the late 60s, and the base for the Catalytica system. Chapter 3 examines the catalytic borylation of alkanes, discovered by Hartwig, whereas chapter 4 provides an updated vision of the alkane dehydrogenation reaction. Chapter 5 covers the oxygenation of C-H bonds, a field of enormous interest with bioinorganic im-plications, and finally chapter 6 presents the functionalization of alkane C-H bonds by carbene or nitrene insertion. The history of C-H bond activation, and the current research described in this book, highlight the current research and present the reader with an outlook of this field which continues to be explored by an increasingly visionary and enthusiastic group of organic, organometallic, biological and physical chemists.

The book about homogeneous catalysis with metal complexes deals with the description of the reductive-oxidative, metal complexes in a liquid phase (in polar solvents, mainly in water, and less in nonpolar solvents). The exceptional importance of the redox processes in chemical systems, in the reactions occuring in living organisms, the environmental processes, atmosphere, water, soil, and in industrial technologies (especially in food-processing industries) is discussed. The detailed practical aspects of the established regularities are explained for solving the specific practical tasks in various fields of industrial chemistry, biochemistry, medicine, analytical chemistry and ecological chemistry. The main scope of the book is the survey and systematization of the latest advances in homogeneous catalysis with metal complexes. It gives an overview of the research results and practical experience accumulated by the author during the last decade.

Masakatsu Shibasaki, Motomu Kanai, Shigeki Matsunaga, and Naoya Kumagai: Multimetallic Multifunctional Catalysts for Asymmetric Reactions.- Takao Ikariya: Bifunctional transition metal-based molecular catalysts for asymmetric syntheses.- Chidambaram Gunanathan and David Milstein: Bond Activation by Metal-Ligand Cooperation: Design of ”Green” Catalytic Reactions Based on Aromatization-Dearomatization of Pincer Complexes.- Madeleine C. Warner, Charles P. Casey, and Jan-E. Bäckvall: Shvo's Catalyst in Hydrogen Transfer Reactions.- Noritaka Mizuno, Keigo Kamata, and Kazuya Yamaguchi: Liquid-Phase Selective Oxidation by Multimetallic Active Sites of Polyoxometalate-Based Molecular Catalysts.- Pingfan Li and Hisashi Yamamoto: Bifunctional Acid Catalysts for Organic Synthesis.- Jun-ichi Ito, Hisao Nishiyama: Bifunctional Phebox Complexes for Asymmetric Catalysis.

This book highlights key advances that have occurred in the field of olefin conversion in recent years. The role of homogenous transition metal catalysts which contain an imine functionality is emphasized; their potential applications in the processing and upgrade of olefins to a wide variety of commodity products of very high industrial value is also explored. On the threshold of the fiftieth anniversary of the Noble Prize to Ziegler and Natta, this book gives a critical summary of the state of the art developments in the fascinating and rapidly developing field of the olefin polymerization, oligomerization, and co-polymerization catalysis.

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.

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 Catalysed Reactions in Ionic Liquids is the first non-edited book on the subject of metal catalyzed reactions in ionic liquids to cover the literature from its origins until early 2005. Following a general introduction to the field of biphasic/multiphasic catalysis, the book moves on to describe the synthesis, the functionalisation, and fundamental properties of ionic liquids relevant to catalysis. It then analyses the catalysed reactions according to their type, encompassing hydrogenation, hydroformylation, oxidation, C-C coupling reactions, metathesis, dimerisation, polymerisation and more. Trends, generalisations, advantages and disadvantages of ionic liquids for specific reaction types are also examined as well as specific processes such as supported ionic liquid phase catalysis, continuous processes using CO2 extraction and nanoparticle catalysis. Metal Catalysed Reactions in Ionic Liquids is of interest to those working in catalysis/green chemistry, in particular to advanced level undergraduate and graduate students and researchers in bi- or multiphasic catalysis using ionic liquids.

The chemist has a vast range of high-tech catalysts to use when working in fine chemical synthesis but the catalysts are generally hard to use and require both time, skill and experience to handle properly. The Catalysts for Fine Chemical Synthesis series contains tested and validated procedures which provide a unique range resources for chemists who work in organic chemistry.'... of great value to synthetic organic chemists...'(The Chemists, Summer 2003) Volume 3 in the series focuses on catalysts for carbon-carbon bond formation and presents practical and detailed protocols on how to use sophisticated catalysts by the'inventors'and'developers'who created them. The combination of protocols and review commentaries helps the reader to easily and quickly understand and use the new high-tech catalysts.

Solid catalysts play a fundamental role in all areas between basic research and industrial applications. This book offers a large amount of information about the preparation of solid catalysts. All types of solid catalysts and all important aspects of their preparation are discussed. The highly topical contributions are written by leading experts in disciplines ranging from solid state, interface and solution chemistry to industrial engineering. The straightforward presentation of the material and the comprehensive coverage make this book an essential and indispensible tool for every scientist and engineer working with solid catalysts.

Homogeneous Catalysis by Metal Complexes, Volume II: Activation of Alkenes and Alkynes reviews and systematizes the chemistry of metal ion activation of alkenes and alkynes. The book presents the migration of? bonds; the oxo reaction; and the hydrosilation of alkenes and alkynes. The text also covers topics on the oxidation of alkenes and alkynes, as well as the multiple insertion reactions of alkenes and alkynes.