"Catalytic Microreactors for Portable Power Generation" addresses a problem of high relevance and increased complexity in energy technology. This thesis outlines an investigation into catalytic and gas-phase combustion characteristics in channel-flow, platinum-coated microreactors. The emphasis of the study is on microreactor/microturbine concepts for portable power generation and the fuels of interest are methane and propane. The author carefully describes numerical and experimental techniques, providing a new insight into the complex interactions between chemical kinetics and molecular transport processes, as well as giving the first detailed report of hetero-/homogeneous chemical reaction mechanisms for catalytic propane combustion. The outcome of this work will be widely applied to the industrial design of micro- and mesoscale combustors.

Qi-Lin Zhou and Jian-Hua Xie: Chiral Spiro Catalysts.- Fuk Loi Lam, Fuk Yee Kwong and Albert S. C. Chan: Chiral Phosphorus Ligands with Interesting Properties and Practical Applications.- Jiang Pan, Hui-Lei Yu, Jian-He Xu, Guo-Qiang Lin: Advances in Biocatalysis: Enzymatic Reactions and Their Applications.- Mei-Xiang Wang: Enantioselective Biotransformations of Nitriles.- Man Kin Wong, Yiu Chung Yip and Dan Yang: Asymmetric Epoxidation Catalyzed by Chiral Ketones.- W. J. Liu, N. Li and L. Z. Gong: Asymmetric Organocatalysis.- Qing-Hua Fan and Kuiling Ding: Enantioselective Catalysis with Structurally Tunable Immobilized Catalysts.- Chang-Hua Ding, Xue-Long Hou: Transition Metal-Catalyzed Asymmetric Allylation.- Jian Zhou and Yong Tang: Enantioselective Reactions with Trisoxazolines.- Xiang-Ping Hu, Duo-Sheng Wang, Chang-Bin Yu, Yong-Gui Zhou, and Zhuo Zheng: Adventure in Asymmetric Hydrogenation: Synthesis of Chiral Phosphorus Ligands and Asymmetric Hydrogenation of Heteroaromtics.

Juan I. Padron and Victor S. Martin: Catalysis by means of Fe-based Lewis acids; Hiroshi Nakazawa*, Masumi Itazaki: Fe-H Complexes in Catalysis; Kristin Schroder, Kathrin Junge, Bianca Bitterlich, and Matthias Beller: Fe-catalyzed Oxidation Reactions of Olefins, Alkanes and Alcohols: Involvement of Oxo- and Peroxo Complexes; Chi-Ming Che, Cong-Ying Zhou, Ella Lai-Ming Wong: Catalysis by Fe=X Complexes (X=NR, CR2); Rene Peters, Daniel F. Fischer and Sascha Jautze: Ferrocene and Half Sandwich Complexes as Catalysts with Iron Participation; Markus Jegelka, Bernd Plietker: Catalysis by Means of Complex Ferrates."

Ruthenium Oxidation Complexes explores ruthenium complexes, particularly those in higher oxidation states, which function as useful and selective organic oxidation catalysts. Particular emphasis is placed on those systems which are of industrial significance. The preparation, properties and applications of the ruthenium complexes are described, followed by a presentation of their oxidative properties and summary of the different mechanisms involved in the organic oxidations (e.g. oxidations of alcohols, alkenes, arenes and alkynes, alkanes, amines, ethers, phopshines and miscellaneous substrates). Moreover, future trends and developments in the area are discussed. This monograph is aimed at inorganic, organic, industrial and catalysis chemists, especially those who wish to carry out specific organic oxidations using catalytic methods.

The chemistry of transition metal carbyne complexes has become a highly attractive field during the past twenty years. In recent years its application to aspects of catalysis and metathesis has gained considerable interest from inorganic as well as organic chemists. In addition, organic synthesis by means of metal carbon multiple bond reagents offers the most sophisticated technology currently available. In consideration of these developments some of Professor E. O. Fischer's former coworkers and colleagues felt obliged to orga nize this NATO Advanced Research Workshop on Transition Metal Carbyne Complexes in the Bavarian Alps. They have been encouraged by the fact that most of the distinguished scientists in the field of metal-carbon multiple bond chemistry had finally agreed to participate and to present stimulating lectures. The organizers of the workshop are deeply grateful to the Scientific Affairs Division of the NATO for the generous financial support of the meeting in Wildbad Kreuth and for the preparation of this book. They also feel indebted to acknowledge the generous support from Wacker-Chemie, BASF, Peroxid-Chemie, Hoechst and Bayer. Finally they thank the staff of the Hanns-Seidel-Stiftung in Wildbad Kreuth for providing a pleasant and stimu lating atmosphere during the meeting."

Knoevenagel Reaction of Unprotected Sugars, By M.-C. Scherrmann; Carbohydrate-Based Lactones: Synthesis and Applications, By N. M. Xavier, A. P. Rauter, and Y. Queneau; Heterogeneously-Catalyzed Conversion of Carbohydrates, By K. De Oliveira Vigier and F. Jerome; Palladium-Catalyzed Telomerization of Butadiene with Polyols: From Mono to Polysaccharides, By S. Bouquillon, J. Muzart, C. Pinel, and F. Rataboul; Monosaccharides, By J.A. Galbis and M.G. Garcia-Martin; Natural Sources, By L. Weignerova and V. K en; Synthesis and Applications of Ionic Liquids Derived from Natural Sugars; By C. Chiappe, A. Marra, and A. Mele"

The use of electrochemical techniques by chemists, particularly those who regard themselves as "inorganic" coordination chemists, has undergone a very rapid growth in the last 15-20 years. The techniques, as dassically applied to inorganic species, had their origins in analytical chemistry, and the methodology had assumed, until the mid 60s, more importance than the chemiStry. However, the growth of interest in coordination compounds (including organometallic complexes) having unusually rich of electron-transfer in bio-inorganic redox properties, and in the understanding species, has propelfed electro-chemistry into the foreground of potentially readily available techniques for application to a very wide range of problems of interest to those chemists. This growth has been fuelled additionally by the availability of relatively cheap equipment of growing sophistication and by an increase in the "inorganic" chemists' general knowledge of physical electrochemistry. In particular, with increasing availability and sophistication of eqUipment, kinetic problems are now being addressed, and the range of electrode types and configuration and solvents has been greatly expanded. Furthermore, the rapid expansion of interest in biological problems has opened new avenues in functionalisation of electrodes, in the development of sensory devices and, in a sense, a return to the analytical base of the science, using novel and multi-disciplinary techniques drawing on synthesis chemistry of and electronic micro-engeneering. The drive towards increasing use microcomputer-controlled data analysis and the development of microeledrodes has opened exciting new avenues for the exploration of chemical reactions involving electron-transfer processes.

In order to adapt the properties of living materials to their biological functions, nature has developed unique polyelectrolytes with outstanding physical, chemical and mechanical behavior. Namely polyampholytes can be suitable substances to model protein folding phenomenon and enzymatic activity most of biological macromolecules due to the presence of acidic and basic groups. The ability of linear and crosslinked amphoteric macromolecules to adopt globular, coil, helix and stretched conformations and to demonstrate coil-globule, helix-coil phase transitions, and sol-gel, collapsed expanded volume changes in relation to internal (nature and distribution of acid and base substituents, copolymer composition, hydrophobicity etc. ) and external (pH, temperature, ionic strength of the solution, thermodynamic quality of solvents etc. ) factors is very important and constantly attracts the attention of theorists and experimentalists because the hierarchy of amphoteric macromolecules can repeat, more or less, the structural organization of proteins. That is why polyampholytes fall within eyeshot of several disciplines, at least polymer chemistry and physics, molecular biology, colloid chemistry, coordination chemistry and catalysis. The main purpose of this monograph is to bridge the gap between synthetic and natural polymers and to show a closer relationship between two fascinating worlds. The first chapter of the book acquaints the readers with synthetic strategy of "annealed", "quenched" and "zwitterionic" polyampholytes. Radical copolymerization, chemical modification and radiation-chemical polymerization methods are thoroughly considered. Kinetics and mechanism of formation of random, alternating, graft, di-block or tri-block sequences is discussed. The second chapter deals with behavior of polyampholytes in solutions.

Intensive research on zeolites, during the past thirty years, has resulted in a deep understanding of their chemistry and in a true zeolite science, including synthesis, structure, chemical and physical properties, and catalysis. These studies are the basis for the development and growth of several industrial processes applying zeolites for selective sorption, separation, and catalysis. In 1983, a NATO Advanced Study Institute was organized in Alcabideche (portugal) to establish the State-of-the-Art in Zeolite Science and Technology and to contribute to a better understanding of the structural properties of zeolites, the configurational constraints they may exert, and their effects in adsorption, diffusion, and catalysis. Since then, zeolite science has witnessed an almost exponential growth in published papers and patents, dealing with both fundamentals issues and original applications. The proposal of new procedures for zeolite synthesis, the development of novel and sophisticated physical techniques for zeolite characterization, the discovery of new zeolitic and related microporous materials, progresses in quantum chemistry and molecular modeling of zeolites, and the application of zeolites as catalysts for organic reactions have prompted increasing interest among the scientific community. An important and harmonious interaction between various domains of Physics, Chemistry, and Engineering resulted therefrom.

The subject of acidity and basicity has enormous economic and technological value while it continues to present significant scientific challenges with prospects for further important technological developments. Historically, technological developments in acidity/basicity have often preceded the scientific understanding of the phenomena involved, certainly in the petroleum industry, a key beneficiarry and user of the concepts of acidity. This process, however, is very expensive and less efficient than developments based on a fundamental understanding of the scientific phenomena involved. This has been recognized over the years and it explains why university, government and industrial laboratories have in the last 50 years devoted large efforts to understanding acidity (and basicity to a lesser extent) so they can gain the technological advantage. The scientific and technological literature on the subject is truly enormous. There have been some very important articles and books on the subject that have attempted to critically review many individual contributions. During the last few years there have been three developments that led us to organize the Advanced Study Institute on which this volume is based: a) Significant developments in the theory of acids and bases; b) Developments in instrumentation that allow the detailed characterization of materials including in-situ conditions relevant to industrial processes; c) The realization that closer coupling of scientific and technological pursuits can lead to greater scientific understanding and better technology. The structure of the ASI reflected the coming-together of these three factors.

The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and alkyne polymerization. The topics of the course were: mechanism of ROMP reactions/ new catalysts for ROMP/ new products by ROMP/ new catalysts for ADMET/ new products by ADMETI degradation of polymer by metathesis reactions/ alkyne polymerization and metathesis/ industrial application of metathesis reactions. The Advanced Study Institute was generously sponsored by the Scientific Affairs Division of NATO and the editor gratefully acknowledges this sponsorship. We also thank the Members of the Local Organizing Committee for their engagement on a successful NATO-AS ."

Olefin metathesis reaction can be considered as one of the most successful organic reactions with many applications in the low molecular weight range and also in the polymer field. The use of catalysts with their selective and effective transformation properties in olefin metathesis I polymerization systems is a growing interest. There has been great effort and competition in developing active and commercially useful catalysts. The main aim of this ASI was to gather several research groups and also the people from industry. to present existing knowledge and latest results in the field. A wide range of topics through homogeneous and heterogeneous aspects have been considered. Attention has been drawn to the metal-carbene and metallacyclobutane complexes as active species, the initiation mechanisms, the stereochemistry and thermodynamics of these reactions. New catalytic systems for the metathesis of alkenes and alkynes and fot' ring opening polymeriZation I block copolymerization reactions have been introduced. Spectroscopic studies for the characteriZation of catalysts, simulation studies explaining the function of chain carrier species and polymer degradation have also been covered. A detailed industrial report concerning the patents and applications in olefin metathesis I cyc1001efin polymerization area, fabrication and derivation has been presented. This volume contains the main lectures and seminars given at the NATO Advanced Study Institute on " Olefin Metathesis and Polymerization Catalysts: Synthesis, Mechanism and Utilization," held at Akcay. Babkesir. Turkey between 10th and 22nd September 1989.

In the last 15 years aqueous organometallic chemistry and catalysis has emerged from being a laboratory curiosity to become an established field of research. Topics reviewed here include mechanistic studies on the effect of water on catalyzed reactions, the preparation of water soluble phosphines as ligands for catalysis, metal catalyzed organic reactions in water (hydrogenation, hydroformylation, carbonylation, olefin metathesis, hydrophosphination, etc.), chiral ligands and enantioselective catalysis, organometallic radical photochemistry in aqueous solutions, bioorganometallic chemistry, organometallic reactions of biopolymers, and catalytic modification of biomembranes. The summary of recent results is supplemented by an assessment of probable future research trends. Audience: Researchers in both academia and industry, as well as graduate students of homogeneous catalysis.

Studies of free radicals on surfaces are of interest for several reasons: the spontaneous or stimulated formation of radicals from adsorbed molecules may represent one possible mechanism for heterogeneous catalysis. In some cases the radicals are ionic, indicating that primary oxidation and reduction reactions occur. Radicals can also be used as probes to investigate diffusion processes on catalytic surfaces. The first direct observations were made more than 30 years ago, but detailed studies of structure, reactions and mobility have only recently become feasible with the advent of powerful spectroscopic techniques, to a great extent developed and used by the contributors to this volume. This comprehensive review describes new trends in the field. Leading experts write about the nature of surface active sites, methods to identify them, and the radicals formed from adsorbed molecules interacting with the surface. The emphasis is on the fundamentals covering thermal, photostimulated and radiation induced reactions as well as diffusion processes. This provides the necessary background for technological applications. This book will be useful to those who are interested in surface chemistry, heterogeneous catalysis as well as those who want to study reactive intermediates in chemical reactions. It is also of interest to scientists in photo and radiation physics and chemistry.

The activation of dioxygen by metal ions has both synthetic potential and biological relevance. Dioxygen is the cleanest oxidant for use in emission-free technologies to minimize pollution of the environment. The book gives a survey of those catalyst systems based on metal complexes which have been discovered and studied in the last decade. They activate molecular oxygen and effect the oxidation of various organic compounds under mild conditions. Much of the recent progress is due to a search for biomimetic catalysts that would duplicate the action of metalloenzymes. Mechanistic aspects are emphasized throughout the book. An introductonary chapter reviews the chemistry of transition metal dioxygen complexes, which are usually the active intermediates in the catalytic reactions discussed. Separate chapters are devoted to oxidation of saturated, unsaturated and aromatic hydrocarbons, phenols, catechols, oxo-compounds, phosphorus, sulfur and nitrogen compounds.

The last two decades have seen a rapid growth in the synthetic processing of both simple and complex molecules, aimed at meeting the needs of society in all aspects of life. Many efforts have been devoted to the development of new biologically active compounds, new materials with innovative properties such as bio-compatibility, new catalysts that allow highly selective transformations, and technologies that facilitate the synthetic pro cesses. This book is a compendium of recent progress in all these aspects of synthetic chemistry. It collects the lectures of the XII International Conference on Organic Synthesis, held in Venice from June 28 to July 2, 1998, in which the present state of art of this discipline has been reported. The topics covered include: combinatorial chemistry, new synthetic methods, stereo selective synthesis, metal-mediated synthesis, and target oriented synthesis. The book collects the contributions, in the mentioned topics, of 43 scientists from 19 different countries. The contributions presented in the Conference as plenary lectures are reported in the first section of the book. Particular attention has been dedicated to combinatorial chemistry, a new and promising methodology for the synthesis of libraries of pharmaco logically interesting compounds in order to allow the automatic pharmacological screening of thousands of compounds. The Conference has dedicated to combinatorial chemistry a mini-symposium in which scientists from academy and companies have described the current trends of this very new technology.

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. Backvall: 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."

The serious study of the reaction mechanisms of transition metal com plexes began some five decades ago. Work was initiated in the United States and Great Britain; the pioneers ofthat era were, inalphabetical order, F. Basolo, R. E. Connick, 1. O. Edwards, C. S. Garner, G. P.Haight, W. C. E. Higgision, E.1. King, R. G. Pearson, H. Taube, M.1. Tobe, and R. G. Wilkins.A larger community of research scientists then entered the field, many of them stu dents ofthose just mentioned. Interest spread elsewhere as well, principally to Asia, Canada, and Europe. Before long, the results ofindividual studies were being consolidated into models, many of which traced their origins to the better-established field of mechanistic organic chemistry. For a time this sufficed, but major revisions and new assignments of mechanism became necessary for both ligand sub stitution and oxidation-reduction reactions. Mechanistic inorganic chemistry thus took on a shape of its own. This process has brought us to the present time. Interests have expanded both to include new and more complex species (e.g., metalloproteins) and a wealth of new experimental techniques that have developed mechanisms in ever-finer detail. This is the story the author tells, and in so doing he weaves in the identities of the investigators with the story he has to tell. This makes an enjoyable as well as informative reading."

It was a great honor for us to organize ChiCat, a symposium devoted to Chiral Reactions in Heterogeneous Catalysis and to be the hostsofmore than 120 scientists coming from everywhere in the industrialized world, to celebrate together one century of existence ofInstitut Meurice. This school was established in 1892when an industrial chemist, named Albert Meurice, decided to educate practical chemists according to the perceived needs ofthe industry ofthat time. This is exactly what we are still trying to do. It is the reason why, thirty years ago, we started a research activity in catalysis, and why we progressively devote this research to the applications of catalysis in the field of fine chemicals. In this respect, we are very close to another initiative of Albert Meurice, who started the first production of synthetic pharmaceuticals in Belgium during World War I. This business later on became a part ofthe Belgian corporation DCB, still very active in pharmaceuticals today. The school created by Albert Meurice merged in the fifties with another school that had been created to meet the same needs in the field of the food industries, mainly distilleries and breweries. This merger was done in the frame of the establishment of CERIA. For people in catalysis, ceria stands for cerium oxide, but for those who engineered the concept, CERIA stood for Center of Education and Research for the Food and Chemical Industries.

Alexander L. Reznichenko and Kai C. Hultzsch: Catalytic -Bond Metathesis Zhichao Zhang, Dongmei Cui, Baoli Wang, Bo Liu, Yi Yang: Polymerization of 1,3-Conjugated Dienes with Lanthanide Precursors Frank T. Edelmann: Homogeneous Catalysis using Lanthanide Amidinates and Guanidinates Tianshu Li, Jelena Jenter, Peter W. Roesky: Rare Earth Metal Post-metallocene Catalysts with Chelating Amido Ligands

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.

This book analyzes conventional fixed-bed reactors such as trickle-bed, bubble (packed) column, and multitubular reactors with regard to process efficiency, design and safety. It is shown that these reactors do not possess any substantial potential for improving industrial processes. Modern concepts in mass transfer, kinetics and process design are applied to process development. In light of the given analysis, new approaches to the development of technologies based on innovative principles are elucidated. For the first time, first-hand knowledge about Two-Zone Model, Oscillation Theory, map of the energy dissipation is presented in full.

The demand for selective organic reactions is growing more acute everyday. Indeed, greater product selectivity has an important impact on energy and resource utilization, in terms of reduced process energy requirements for product separation and purification, in terms of low-value by-products, and in terms of environmental acceptance and compatibility. Moreover, more and more chemicals, especially pharmaceuticals, have to be sold in an optically active form. The search for selectivity constitutes a tremendous challenge for the chemists. In the last two decades, homogeneous transition metal based catalysis has emerged as one of the most promising tools for obtaining selectivity. In connection with developments in this area, this book contains updated and expanded versions of most of the lectures presented at a Cornett course held in Trieste (Italy) in 1989 and sponsored by the European Community. A primary aim is to cultivate a deeper understanding of the parameters that govern the selectivities and stimulate a wider utilization of transition metal based catalysis in organic synthesis. All aspects of selectivity, chemo-, regio-, stereo- and enantioselectivity are considered and illustrated by applications in various fields or organic synthesis. The impact of catalysis in oxydation, reduction, carbonylation reactions, carbene chemistry, in Ni and Pd promoted dimerizations, oligomerizations as well as fonctionalisations is stressed, quite often with special emphasis laid on reaction mechanisms. In this aspect, the last chapter examplifies the interest of high pressure NMR and IR when investigating the nature of reaction intermediates in homogeneous reactions.

The focus of this thesis is the computational modelling of transition metal bimetallic (nanoalloy) clusters. More specifically, the study of Pd-Pt, Ag-Pt, Au-Au and Pd-Au as a few tens of atoms in the gas phase. The author used a combination of global optimization techniques - coupled with a Gupta-type empirical many-body potential - and Density Functional Theory (DFT) calculations to study the structures, bonding and chemical ordering, as well as investigate the chemisorptions of hydrogen and carbon monoxide on bimetallic clusters. This research is highly relevant to experimental catalytic studies and has resulted in more than seven publications in international journals.

217 2. COPOLYMERIZATION OF PROPENE OR HIGHER I-ALKENES WITH 218 CARBON MONOXIDE 2. 1. Ligands and polymerization conditions 218 2. 2. Spiroketal formation 221 2. 3. Enantioselectivity 222 2. 4. Higher I-Alkenes 226 3. COPOLYMERIZATION OF STYRENE OR ITS DERIVATIVES WITH 226 CARBON MONOXIDE 4. COPOLYMERIZATION OF OTHER OLEANS WITH CARBON MONOXIDE 230 5. ASYMMETRIC TERPOLYMERIZATION OF MORE THAN Two KINDS OF 232 OLEFINS WITH CARBON MONOXIDE 6. POLYKETONE CONFORMATION 233 7. CONCLUSION 234 Chapter 8. Chain Propagation Mechanisms 237 Ayusman Sen 1. INTRODUCTION 237 2. PALLADIUM (II) BASED SYSTEMS 238 3. NICKEL (II) BASED SYSTEMS 256 4. RHODIUM (I) BASED SYSTEMS 257 5. CONCLUSION 261 Chapter 9. Theoretical Studies on Copolymerization of Polar Monomers 265 Peter Margl, Artur Michalak, and Tom Ziegler 1. INTRODUCTION 265 2. COPOLYMERIZATION OF CARBON MONOXIDE WITH ETHYLENE 267 2. 1. Experimental and calculated rates for the insertion processes for 267 copolymerization catalysed by Pd(II) systems. 2. 2. A more detailed look at the productive and unproductive cycles 270 in copolymerization catalysed by Pd(II) complexes. 2. 2. 1. The productive cycle 270 2. 2. 2. C2H4 misinsertion into an ethylene terminated polyketone 275 chain 2. 3. Experimental and calculated rates for the insertion processes for 277 alternating copolymerization catalyzed by Ni(II) systems 3. COPOLYMERIZATION OF OLEFINS WITH POLAR MONOMERS OTHER 280 THAN CO 3. 1. Preferred binding mode of oxygen containing monomers 282 3. 2. Preferred binding mode of nitrogen containing monomers 285 3. 3.