1. INTRODUCTION Although quite spectacular results have been obtained in the last few decades in the field of homogeneous transition metal catalyzed transformations of olefins and alkynes [1], reactions which could lead to heterocycles have been partly neglected. An obvious reason for this is that substrates containing heteroatoms such as N, 0 or S could coordinate the metal and suppress the catalytic activity. Nevertheless, some interesting early examples of transition-metal-catalyzed syntheses of heterocyclic compounds have been reported and these have been reviewed by C. W. Bird [2] . More recently the incorporation of CO , which enables esters and lactones 2 to be synthesized from olefinic starting materials, has begun to attract attention (see, for example, ref. [3]). The dominant role of palladium as the catalyst for the formation of O-containing heterocycles has been suggested to be associated with the relatively low strength of the Pd-O bond. Among the first examples of a nitrogen-containing heterocycle to be formed by homogeneous catalysis is the triazine shown in Equation 1 which is the product of the trimerization of benzonitrile in the presence of iron penta carbonyl or Raney nickel [4] .

As nucleophiles, simple alkenes are typically so unreactive that only highly active electrophiles, such as carbocations, peroxides, and halogens will react with them. For the generation of carbon-carbon bonds, milder methods will often be required. Fortunately, it is possible to increase the reactivity of alkene-type p-nucleophiles by introducing electron-donating substituents. Substitution of one H with an OH or OR gives an enol or a vinyl ether, which are already much better nucleophiles. Using nitrogen instead of oxygen, one obtains even better nucleophiles, enamines. Enamines are among the most reactive neutral carbon nucleophiles, exhibiting rates that are even comparable to some charged nucleophiles, such as enolates [1, 2]. Most enamines, unfortunately, are sensitive to hydrolysis. The parent enamine, N,N-dimethylvinylamine, has in fact been prepared [3], but appears to be uns- ble. Enamines of cyclic ketones and many aldehydes can readily be isolated, however [4-7]. The instability of enamines might at first appear to diminish the utility of enamines as nucleophiles, but actually this property can be viewed as an added benefit: enamines can be readily and rapidly generated catalytically by using a suitable amine and a carbonyl compound. The condensation of aldehydes or ketones with amines initially affords an imine or iminium ion, which then rapidly loses a proton to afford the corresponding enamine (Scheme 1).

Some years ago, I agreed to contribute a volume to the Academic Press 'Organo metallic Chemistry' series - the metals to be covered were rhodium and iridium. Initially, my plan was to discuss both the fundamental organometallic chemistry and applications in organic synthesis. When the first draft of the manuscript was complete, it was apparent that I had exceeded my allowance of pages by a huge amount. It was then that I decided that the catalysis section warranted separate treatment. I am grateful to Reidel for agreeing to publish this volume on Homogeneous Catalysis with Compounds of Rhodium and Iridium as part of their 'Catalysis by Metal Complexes' series. The material I had for the original Academic Press project covered the litera ture to the end of 1978. I decided to update this to the end of 1982 with a few key references from 1983. It is some measure of the rate of progress in this field that the number of references almost doubled during this revision."

In recent years, the liquid phase oxidation of organic substrates using transition metal compounds as catalysts has become a profitable means of obtaining industrially important chemicals. Millions of tons of valuable petrochemicals are produced in this manner annually [1]. Typical examples of such processes are the production of vinyl acetate or acetaldehyde via the Wacker process, equations (1) and (2); the Mid Century process for the oxidation of methyl aromatics, such as p-xylene to tereph thalic acid, equation (3); and the production of propylene oxide from propylene using alkyl hydroperoxides, equation (4). PdCI , CuCI 2 2 (1) CH2 = CH2 + 1/2 O2 -H 0 ~ CH3CHO 2 (2) Co(OAcjz ~ (3) (4) The vast majority of liquid phase transition metal catalyzed oxidations of organic compounds fall into these three broad categories: (a) free radical autoxidation reactions, (b) reactions involving nucleophilic attack on coordinated substrate such as the Wacker process, or (c) metal catalyzed reactions of organic substrates with hydroperoxides. Of these three classes of oxidations only the first represents the actual interaction of dioxygen with an organic substrate. The function of oxygen in the Wacker process is simply to re-oxidize the catalyst after each cycle [2].

This volume contains the lectures presented at the Advanced Study Institute on "Chemistry and Chemical Engineering of Catalytic Solid Fuel Conversion for the Production of aean Synthetic Fuels" which was held at Ak;ay, Edremit, Tiirkiye, between July 21 and August 3, 1991. The book includes 23 chapters originally written for the meeting by distinguished scientists an technologists in the field. l would like to acknowledge the contribution of each of the authors in the book. Their efforts have shed light on our understanding in coal science research and better utilization of coal. Three main subjects: structure and reactivity of coal; cleaning of coal and its products, and factors affecting environmental balance of energy usage and solutions for future, were discussed in the Institute and these are presented under six groups in the book. I hope that of great use to research workers from academic and industrial background. the book will be Many people contributed to the success of the Institute on which this volume was based. I take this occasion to thank my colleagues who lectured in the Institute, both for their efforts during the two weeks and their expertly prepared lecture notes that reached to me in time. The Institute was generously sponsored by the Scientific and Environmental Affairs Dh.ision of the NATO and their contribution is deeply acknowledged."

1. Introduction. There is much interest in the general subject of porous inorganic materials with respect to their use as sorbents or catalysts. Such inorganic solids may be microporous, mesoporous or macroporous according to the sizes of the pores within the solid. Often there is a range of pore sizes within any given solid and so there is special interest in the synthesis, characterisation and application of porous inorganic solids with well defined pores. Pores of diameter larger than 50 nm are generally termed macropores. Those with diameters of less than 2 nm are micropores and pores of intermediate size are called mesopores. Solids, which contain only mesopores, are correctly called mesoporous but very often there is a combination of different types of porosities within one given solid. The synthesis, characterisation and application of microporous solids is much more advanced than is the case with mesoporous substances. Moreover, the synthesis of crystalline mesoporous materials is one clear goal for the future but which has not been attained so far. Consequently, it is of interest to examine the current state of our knowledge of microporous materials and to examine how this may apply to mesoporous materials. Both catalytic and sorption processes could benefit from studies of mesoporous solids because the mesopores could permit diffusion of larger reactants or products than is the case in microporous materials. 2.

3.1.1 ?-Conjugated Materials ?-conjugated polymers (CPs) and oligomers are materials with an extended ?-system along the backbone. The materials possess many remarkable prop- ties, including high charge carrier mobilities, electrical conductivities (doped), electrochromism, and electroluminescence [1]. These properties have been taken advantage of in exploration of potential applications including in ch- ical sensors, light-emitting devices, and ?eld-effect transistors. Many efforts have been devoted to synthesizing new conjugated polymers and oligomers in an effort to increase their processibility, optimize the desirable properties, and explore new properties. In Fig. 3.1 are shown examples of some of the CPs that have been prepared and studied. Coupling ?-conjugated materials to metal complexes gives hybrid mate- als in which the properties of the metal complex may be coupled to those of the conjugated backbone [2]. For example, these materials could be used in energy-harvesting devices such as solar cells or polymer-based light-emitting devices,wherehighchargecarrier mobilities of theconjugatedmaterialmay be combined with either the light-absorbing or emitting metal groups, giving improved device performance [3, 4]. In addition to an electronic role, metal complexes may also be used to geometrically orient ?-conjugated materials in speci?c three-dimensional arrangments in the solid state. Careful conside- tion of theelectronicinteractionsand excitedstatesisnecessary for thedesign of functional materials of this type.

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.

The use of phosphine derivatives has historically induced the tremendous development of catalysis (both non-asymmetric and asymmetric). Although the chemistry of amines is more documented, the use of nitrogen-containing ligands only appeared recently. Nevertheless, during the last ten years, the results describing chiral diamine preparations and their uses in asymmetric catalysis and synthesis are increasing faster than their phosphorus counterparts. The reader will find in this volume the most recent methods for the synthesis of chiral diamines as well as their applications in asymmetric catalysis of CC bond formation. Particular attention will be given to spartein and derivatives of such diamines. Recently, the particular properties and the chemistry of amines allowed to obtain catalysts easy to separate and recycle and new types of ligands such as diaminocarbenes, ureas and thioureas. Finally, the complexing properties of some diamines allowed the formation of complexes with chirality "at the metal " which is of major theoretical interest and presents numerous potential applications.

Photosensitization and photocatalysis refer to processes by which permanent chemical transformations are induced on substrates (organic/inorganic) by radiation to which the substrates themselves are transparent. Such transformations can be highly specific, very efficient, and occur under mild conditions. Herein lies the power of photochemical methods for possible applications in the field of conversion and storage of solar energy. This book provides a recent survey of the progress in this important area in catalysis, with an emphasis on inorganic complexes and organometallic compounds as the key light aborbers. The book is organized in three parts: fundamentals, followed by applications. Discussions cover a wide variety of photosensitized or photocatalyzed reactions: decomposition of water, reduction of CO2 and CO; spectral sensitization in photoelectrochemical cells; transformations (oxidation, reduction, isomerization, hydrogenation, dehydrogenation, carbonylation, etc.) of organics such as alkanes, alkenes, alcohols, etc. In view of the variety of systems (sensitizers, substrates) and the topics covered, the volume is unique in the field of photochemistry and will appeal to academic and industrial researchers in various subdisciplines of chemistry, material science and catalysis.

Hydrotreating catalysis with transition metal sulphides is one of the most important areas of industrial heterogeneous catalysis. The present book deals with the chemical and catalytic aspects of transition metal sulphides, focusing on their use in hydrotreating catalysis. The book?'s 12 chapters present reviews of solid-state, coordination and organometallic chemistry, surface science and spectroscopic studies, quantum chemical calculations, catalytic studies with model and real catalysts, as well as refinery processes. A presentation of state-of-the-art background to pertinent work in the field. Can be used as an introduction to the chemical and catalytic properties of transition metal sulphides as well as an advanced level reference.

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.

This book highlights cyclization via carbopalladation and acylpalladation and Heck-pericyclic sequences. They discuss p-allyl palladium-based cascade reactions, Michael-type additions as an entry to transition-metal-promoted cyclizative transformations, and sequential or consecutive palladium-catalyzed processes, and show Pauson-Khand cascades, metal-catalyzed cyclizations of acyclic precursors, as well as cascade and sequential ruthenium-catalyzed transformations. This is a comprehensive overview of an exciting and highly dynamic, and innovative methodological concept.

Chemical Kinetics and Reaction Dynamics brings together the major facts and theories relating to the rates with which chemical reactions occur from both the macroscopic and microscopic point of view. This book helps the reader achieve a thorough understanding of the principles of chemical kinetics and includes:

• Detailed stereochemical discussions of reaction steps
• Classical theory based calculations of state-to-state rate constants
• A collection of matters on kinetics of various special reactions such as micellar catalysis, phase transfer catalysis, inhibition processes, oscillatory reactions, solid-state reactions, and polymerization reactions at a single source.

The growth of the chemical industry greatly depends on the application of chemical kinetics, catalysts and catalytic processes. This volume is therefore an invaluable resource for all academics, industrial researchers and students interested in kinetics, molecular reaction dynamics, and the mechanisms of chemical reactions.

The subject of dioxygen activation and homogeneous catalytic oxidation by metal complexes has been in the focus of attention over the last 20 years. The widespread interest is illustrated by its recurring presence among the sessions and subject areas of important international conferences on various aspects of bioinorganic and coordination chemistry as well as catalysis. The most prominent examples are ICCC, ICBIC, EUROBIC, ISHC, and of course the ADHOC series of meetings focusing on the subject itself. Similarly, the number of original and review papers devoted to various aspects of dioxygen activation are on the rise. This trend is due obviously to the relevance of catalytic oxidation to biological processes such as dioxygen transport, and the action of oxygenase and oxidase enzymes related to metabolism. The structural and functional modeling of metalloenzymes, particularly of those containing iron and copper, by means of low-molecular complexes of iron, copper, ruthenium, cobalt, manganese, etc., have provided a wealth of indirect information helping to understand how the active centers of metalloenzymes may operate. The knowledge gained from the study of metalloenzyme models is also applicable in the design of transition metal complexes as catalytsts for specific reactions. This approach has come to be known as biomimetic or bioinspired catalysis and continues to be a fruitful and expanding area of research.

Heterogeneous catalysis is a fascinating and complex subject of utmost importance in the present day. Its immense technological and economical importance and the inherent complexity of the catalytic phenomena have stimulated theoretical and experimental studies by a broad spectrum of scientists, including chemists, physicists, chemical engineers, and material scientists. Computational and theoretical techniques are now having a major impact in this field. This book aims to illustrate and discuss the subject of heterogeneous catalysis and to show the current capabilities of the theoretical and computational methods for studying the various steps (diffusion, adsorption, chemical reaction) of heterogeneous catalytic process involving zeolites, metal oxides, and transition metal surfaces. The book covers: the use of techniques of computational chemistry to simulate zeolites, metallic and bimetallic surfaces, and oxide-supported metals; the impact of simulation methods on the understanding of the diffusion and adsorption of molecules and cations within the pores of zeolites, and also on the adsorption of molecules on metal and metal-oxide surfaces; and the applications of quantum-mechanical methods to the study of the reaction mechanism and pathways of the adsorbed molecules. This book is recommended primarily to scientists and graduate students conducting research in the fields of heterogeneous catalysis and surface science. It will also be valuable to advanced undergraduate students wishing to become acquainted with the latest developments in these exciting fields of research, and to experimentalists seeking theoretical support for interpreting their results.

This book covers a significant number of R&D projects, performed mostly after 2000, devoted to the understanding and prevention of performance degradation processes in polymer electrolyte fuel cells (PEFCs). The extent and severity of performance degradation processes in PEFCs were recognized rather gradually. Indeed, the recognition overlapped with a significant number of industrial dem- strations of fuel cell powered vehicles, which would suggest a degree of technology maturity beyond the resaolution of fundamental failure mechanisms. An intriguing question, therefore, is why has there been this apparent delay in addressing fun- mental performance stability requirements. The apparent answer is that testing of the power system under fully realistic operation conditions was one prerequisite for revealing the nature and extent of some key modes of PEFC stack failure. Such modes of failure were not exposed to a similar degree, or not at all, in earlier tests of PEFC stacks which were not performed under fully relevant conditions, parti- larly such tests which did not include multiple on-off and/or high power-low power cycles typical for transportation and mobile power applications of PEFCs. Long-term testing of PEFCs reported in the early 1990s by both Los Alamos National Laboratory and Ballard Power was performed under conditions of c- stant cell voltage, typically near the maximum power point of the PEFC.

Summarizing the emerging field of N-heterocyclic carbenes used in organocatalysis, this is an excellent overview of the synthesis and applications of NHCs focusing on carbon-carbon and carbon-heteroatom bond formation. Alongside comprehensive coverage of the synthesis, characteristics and applications, this handbook and ready reference also includes chapters on NHCs for polymerization reactions and natural product synthesis.

Green Chemistry is an inventive science based on fundamental research towards the development of new sustainable chemical processes. There is a great need to create a new type of chemistry focused on a new production system, in order to prepare the younger generation to get a greener future.

The globalization pushes the chemistry community to adopt ethical issues. In this prospect Green Chemistry can achieve the approval of the society by teaching students to be confident in science and at the same time by convincing people that it is possible to attain technological development with respect and care for the environment we live in. This is why it is of foremost importance that education and fundamental research remain strictly connected, so that democracy and development can grow and progress side by side.

This book has been prepared to extend the knowledge of Green Chemistry not disregarding, however, the industrial interest. It is the result of the effort to put together and share the expertise of leading practitioners in the field of Green Chemistry.

The Interuniversity Consortium 'Chemistry for the Environment' is a non-profit organisation established in 1993 in Italy. At present it includes 31 member universities and 80 research units.

Apply an Omnibus of Knowledge from Leaders in the Field The unexpected diversity of topics presented at previous gatherings forced organizers of 2008's 22nd Conference on Catalysis of Organic Reactions to expand its format to reflect the remarkable current degree of specialization in the field. Catalysis of Organic Reactions contains a compilation of papers presented at the event, and subsequently, few books will be able to match the breadth and depth of its content. Featuring papers by respected scientists from academia, industry, and the governmental research-and-development sector, it covers various aspects of the production, sale, and use of catalysts for practical purposes. Articles concentrate on the general area of catalyzed synthesis, emphasizing the production of organic chemicals. With a focus on application rather than theory, the dominant theme is the traditionally practiced area of heterogeneous catalysis. Topics include: Hydrogenation and hydrogenolysis C-C coupling Amination and oxidation (including the precious metal, supported base metal, and sponge metal, Raney process, and homogeneous catalyst types) End uses of products, including industrial petrochemicals, fine chemicals, and pharma intermediates Those working with applied catalysis will benefit greatly from this consolidation of insights and reviews of the latest developments in the field. Each of the papers presented were edited by ORCS members, drawn from both academia and industry, and peer-reviewed by experts in related fields of study.

During the last decade we have been witness to several exciting achievements in electron crystallography. This includes structural and charge density studies on organic molecules complicated inorganic and metallic materials in the amorphous, nano-, meso- and quasi-crystalline state and also development of new software, tailor-made for the special needs of electron crystallography. Moreover, these developments have been accompanied by a now available new generation of computer controlled electron microscopes equipped with high-coherent field-emission sources, cryo-specimen holders, ultra-fast CCD cameras, imaging plates, energy filters and even correctors for electron optical distortions. Thus, a fast and semi-automatic data acquisition from small sample areas, similar to what we today know from imaging plates diffraction systems in X-ray crystallography, can be envisioned for the very near future. This progress clearly shows that the contribution of electron crystallography is quite unique, as it enables to reveal the intimate structure of samples with high accuracy but on much smaller samples than have ever been investigated by X-ray diffraction. As a tribute to these tremendous recent achievements, this NATO Advanced Study Institute was devoted to the novel approaches of electron crystallography for structure determination of nanosized materials.

This volume brings together the work of both theoreticians and experimentalists on the synthesis of nanoparticles and their use in catalytic reactions. Heterogeneous catalysis is a core area of contemporary physical chemistry posing major fundamental and conceptual challenges, and nanoparticles are ubiquitous in many heterogeneous catalysts, therefore it is now opportune to focus a Faraday Discussion on key aspects of their synthesis, characterisation and use. This Faraday Discussion will explore the modern methods being used to design, synthesise and characterize nanoparticles and how these bridge across the disciplines of physical science and chemical engineering. The core aim of this discussion meeting is to develop a fundamental understanding of these crucial aspects of catalytic science, especially relating to nanoparticle synthesis and use in catalytic reactions, knowledge of which is essential for the design of new catalysts.

Fuel Cells have become a potentially highly efficient sustainable source of energy and electricity for an ever-demanding power hungry world. The two main types of fuel cells ripe for commercialisation are the high temperature solid oxide fuel cell (SOFC) and the low temperature polymer electrolyte membrane fuel cell (PEM). The commercial uses of which include, but are not limited to, military, stand-by power, commercial and industrial, and remoter power. However, all aspects of the electricity market are being considered.

This book has brought together a team of world-renowned experts in all aspects of fuel cell development for both SOFC and PEM in a workshop environment. The workshop held between June 6-10, 2004 was held in the capital city of the Ukraine, Kiev. The reason for the venue was that Ukraine is the third largest resource of zircon sands, a major source of material for the solid oxide fuel cell. Ukraine is looking at undertaking a very large effort in the solid oxide fuel cell arena, and hopes, one day, to be an international player in this market, and this book is an outcome from the workshop. The book focuses on the issues related to fuel cells, particularly the state-of-the-art internationally, the issues that were of particular interest for getting fuel cells fully commercialized, and advances in fuel cell materials and technology. The focus was on all types of fuel cells, but the emphasis was particularly on solid oxide fuel cells (SOFC), due to their importance to the host country. The book is an essential reference to researchers, academics and industrialists interested in up-to-date information on SOFC and PEM development.

High throughput experimentation has met great success in drug design but it has, so far, been scarcely used in the field ofcatalysis. We present in this book the outcome of a NATO ASI meeting that was held in Vilamoura, Portugal, between July 15 and 28, 2001, with the objective of delineating and consolidating the principles and methods underpinning accelerated catalyst design, evaluation, and development. There is a need to make the underlying principles of this new methodology more widely understood and to make it available in a coherent and integrated format. The latter objective is particularly important to the young scientists who will constitute the new catalysis researchers generation. Indeed, this field which is at the frontier offundamental science and may be a renaissance for catalysis, is one which is much more complex than classical catalysis itself. It implies a close collaboration between scientists from many disciplines (chemistry, physics, chemical and mechanical engineering, automation, robotics, and scientific computing in general). In addition, this emerging area of science is also of paramount industrial importance, as progress in this area would collapse the time necessary to discover new catalysts or improve existing ones.

hemistry is the science about breaking and forming of bonds between atoms. One of the most important processes for organic chemistry is breaking bonds C-H, as well as C-C in various compounds, and primarily, in hydrocarbons. Among hydrocarbons, saturated hydrocarbons, alkanes (methane, ethane, propane, hexane etc. ), are especially attractive as substrates for chemical transformations. This is because, on the one hand, alkanes are the main constituents of oil and natural gas, and consequently are the principal feedstocks for chemical industry. On the other hand, these substances are known to be the less reactive organic compounds. Saturated hydrocarbons may be called the "noble gases of organic chemistry" and, if so, the first representative of their family - methane - may be compared with extremely inert helium. As in all comparisons, this parallel between noble gases and alkanes is not fully accurate. Indeed the transformations of alkanes, including methane, have been known for a long time. These reactions involve the interaction with molecular oxygen from air (burning - the main source of energy!), as well as some mutual interconversions of saturated and unsaturated hydrocarbons. However, all these transformations occur at elevated temperatures (higher than 300-500 DegreesC) and are usually characterized by a lack of selectivity. The conversion of alkanes into carbon dioxide and water during burning is an extremely valuable process - but not from a chemist viewpoint.