This book brings together and makes easily accessible data on flash points pres- ently listed in the standard references, plus many values measured in American indus- trial laboratories and European data as represented by the Fluka catalog and by values given in Nabert and Schoen. It is a collection that should be useful to those involved in manufacturing, handling, and shipping the many organics and organometallics now in production. The author would like to thank David Harvey, President, and Chuck Pouchert, of Aldrich Chemical Company, for permission to use their material and for provid- ing a computer printout of some six thousand chemicals listed in the Aldrich cata- log. Flash points for most of these chemicals were measured in the Aldrich laboratories and are not available elsewhere. Thanks are due also to Dr. Marjan Bace of Elsevier Science Publishing Co., Inc., who recognized the need for a handbook on flash points and handled the pub- lishing arrangements. Particular thanks go to my wife, Mary, who prepared the entire camera-ready manuscript. Richard M. Stephenson The University of Connecticut Storrs, Connecticut December, 1986 v Introduction Flash points are of particular importance to those involved with the handling and ship- ping of organics and organometaliics. As each country has its own shipping regula- tions, this can be a real problem for international shippers. Many flash points have been determined by individual chemical manufacturers in answer to their own needs.

An overview of modern organometallic thermochemistry, made by some of the most active scientists in the area, is offered in this book. The contents correspond to the seventeen lectures delivered at the NATO ASI Energetics of Organometallic Species (Curia, Portugal, September 1991), plus three other invited contributions from participants of that summer school. These papers reflect a variety of research interests, and discuss results obtained with several techniques. It is therefore considered appropriate to add a few preliminary words, attempting to bring some unity out of that diversity. In the first three chapters, results obtained by classical calorimetric methods are described. Modern organometallic thermochemistry started in Manchester, with Henry Skinner, and his pioneering work is briefly surveyed in the first chapter. The historical perspective is followed by a discussion of a very actual issue: the trends of stepwise bond dissociation enthalpies. Geoff Pilcher, another Manchester thermochemist, makes, in chapter 2, a comprehensive and authoritative survey of problems found in the most classical of thermochemical techniques - combustion calorimetr- applied to organometallic compounds. Finally, results from another classical technique, reaction-solution calorimetry, are reviewed in the third chapter, by Tobin Marks and coworkers. More than anybody else, Tobin Marks has used thermochemical values to define synthetic strategies for organometallic compounds, thus indicating an application of thermochemical data of which too little use has been made so far.

For several years, the two parallel worlds of Molecular Conductors in one hand and Molecular Magnetism in the other have grown side by side, the former essentially based on radical organic molecules, the latter essentially based on the high spin properties of metal complexes. Over the last few years however, organometallic derivatives have started to play an increasingly important role in both worlds, and have in many ways contributed to open several passages between these two worlds. This volume recognizes this important emerging evolution of both research areas. It is not intended to give a comprehensive view of all possible organometallic materials, and polymers for example were not considered here. Rather we present a selection of the most recent research topics where organometallic derivatives were shown to play a crucial role in the setting of conducting and/or magnetic properties in crystalline materials. First, the role of organometallic anions in tet- thiafulvalenium-based molecular conductors is highlighted by Schlueter, while Kubo and Kato describe very recent ortho-metalated chelating ligands appended to the TTF core and their conducting salts. The combination of conducting and magnetic properties and the search for p-d interactions are analyzed in two comp- mentary contributions by Myazaki and Ouahab, while Valade focuses on the only class of metal bis(dithiolene) complexes to give rise to superconductive molecular materials, in association with organic as well as organometallic cations.

Born and initially developed in various industrial laboratories, mainly in U.S.A. and Gennany, homogeneous phase catalytic carbon monoxide hydrogenation and alcohols and their derivatives carbonylation and homologation, have generally been considered and reviewed separately in the course of their 40 years history without concern for common aspects in the chemical transfonnations and in catalysis. Thanks to researchers of Japanese companies participating in the National C 1 Chemistry Project (1980-1987) the scientific and technical approaches in this field have been unified and applied in parallel, in the light of some common aspects of the chemical reactions and mechanisms. Now, at a moment when research seems becahned, a general presentation and discussion of the most recent topics might be an useful basis for further development of this chemistry. To delimit and simplify the discussion of the chemical aspects and the nature of the catalysts involved, the present review is limited to reactions employing homogeneous metal complexes for the direct conversion of syngas to oxygenates and to the hydrocarbonylation of these last to homologous derivatives. Since the previous practically contemporary reviews by Dombek [in Adv. Organomet. Chern. (1983)] on CO hydrogenation and by the present authors [in Asp.Homog.Catal.(Reidel Pu.l984)] on alcohol homologation fully cover the literature up to 1982, here we mainly refer to work done after 1982, and consider the cited reviews as covering the historical development of research in the 1940- 1980 period.

Contents: Kilian Muniz: Transition Metal Catalyzed Electrophilic Halogenation of C-H bonds in alpha-Position to Carbonyl Groups; Arkadi Vigalok * and Ariela W Kaspi: Late Transition Metal-Mediated Formation of Carbon-Halogen Bonds; Paul Bichler and Jennifer A. Love*: Organometallic Approaches to Carbon-Sulfur Bond Formation; David S. Glueck: Recent Advances in Metal-Catalyzed C-P Bond Formation; Andrei N. Vedernikov: C-O Reductive Elimination from High Valent Pt and Pd Centers; Lukas Hintermann: Recent Developments in Metal-Catalyzed Additions of Oxygen Nucleophiles to Alkenes and Alkynes; Moris S. Eisen: Catalytic C-N, C-O and C-S bond formation promoted by organoactinide complexes."

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.

The design, -synthesis, and selective pyrolytic conversion of organo metallic precursdrs to materials of high purity or specific morphology (for electronic or optical applications), high strength and/or high-temperature stability (for structural or refractory applications) represents a poten tial area of extreme growth at the overlap of chemistry and materials science (materials chemistry). Research in this area is likely to have considerable impact at both the academic and societal levels because it will require development of scientific expertise in areas currently not well understood. Examples include: (1) The thermodynamics of molecular rearrangements in organometallic molecules at temperatures above 200 DegreesC; (2) The electronic properties of amorphous ceramic materials; (3) The phys icochemical properties of ceramic molecular composites; and (4) The optical properties of multicomponent glasses made by sol-gel processing. The opportunity to establish the scientific principles needed to pursue useful research goals in "materials chemistry" requires communica tion between chemists, ceramists, metallurgists, and physicists. To date, there have been few opportunities to create an environment where such communication might occur. The objective of this NATO Advanced Research Workshop was to promote discussions between experts in the varibus disci plines aligned with "materials chemistry. " These discussions were intended to identify the scope and potential rewards of research efforts in the development of: Custom-designed precursors to common and exotic materials, methods of selectively transforming these precursors in high yield to the desired material, and methods of characterizing the final products.

The rate of advance in areas of science is seldom constant. Usually certain fields effloresce with activity because of the ealization that solutions are possible to long standing important problems. So it is now with asymmetric catalysis, a field which promises to change profoundly the strategic thinking of synthetic chemists. As this Report will show, reagents which can induce catalytic enantiocontrol of chemical transformations could represent the ultimate synthetic method. Nearly all synthetic strategies of complex molecules involve steps which require enantiocontrol and, in many cases, a specific catalytic transformation embodying enan tiocontrol has enormous advantages in terms of the rate and economy of the reaction. Because asymmetric catalysis is in a formative stage, workers with different backgrounds have joined the field. This Workshop had representatives with organometallic, organic, structural, kinetic, enzymatic, microbiological and industrial backgrounds. Each had his own perspective and this Report represents a consensus of this group of eleven people. The result is probably as compre hensive and balanced a view of the subject as is possible at present. It is hoped that those who have until now had but a glancing interest in asymmetric catalysis will find this Report a useful indication of its present state. We believe that asymmetric catalysis will have an increasing impact on the development of chemistry and will eventually dominate much of synthetic and industrial chemistry."

The Joint Meeting comprisIng the 3rd International Symposium on Clathrate Compounds and Molecular Inclusion Phenomena and the 2nd International Symposium on Cyclodextrins was held on 23-27 July, 1984, in Tokyo, Japan. It was organized by the Japan Association for Inclusion Chemistry together with the International Organization Committee, with the auspices of sixteen societies and associations in Japan. This event was the first joint meeting with the hope of unifying the above two symposia. The program of the symposium consisted of 142 papers, including 14 invited papers. The invited papers and some selected topics were presented verbally, and all the other 118 papers were displayed in poster sessions. The symposium was held at Hoshi University in Tokyo. Due to the multidisciplinary nature of the subjects treated, the scope and subjects were grouped into two parts. In the first group, the chemistry of cyclodextrins, synthetic organic hosts, inorganic and metal complex hosts and layered hosts were treated. In the second group applications in various fields, biomimetic aspects, physicochemical aspects, selectivity, stereo-specificity and other aspects were discussed. The scientific sessions were carried out in a really vivid atmosphere. The number of participants viz 50 from 19 overseas countries and 253 domestic partici pants exceeded our expectation."

Many sections of this revised edition have been completely rewritten to take into account the enormous advances in recent years. The book's strenth lies in covering all the main group and transition metals in sufficient depth to give the student a good understanding of the subject.

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).

Barry Trost: Transition metal catalyzed allylic alkylation.- Jeffrey W. Bode: Reinventing Amide Bond Formation.- Naoto Chatani and Mamoru Tobisu: Catalytic Transformations Involving the Cleavage of C-OMe Bonds.- Gregory L. Beutner and Scott E. Denmark: The Interplay of Invention, Observation and Discovery in the Development of Lewis Base Activation of Lewis Acids for Catalytic Enantioselective Synthesis.- David R. Stuart and Keith Fagnou: The Discovery and Development of a Palladium(II)-Catalyzed Oxidative Cross-Coupling of Two Unactivated Arenes.- Lukas Goossen and Kathe Goossen: Decarboxylative Cross-Coupling Reactions.- A. Stephen K. Hashmi: Gold-Catalyzed Organic Reactions.- Ben List: Developing Catalytic Asymmetric Acetalizations.- Steven M. Bischof, Brian G. Hashiguchi, Michael M. Konnick, and Roy A. Periana: The De NovoDesign of CH Bond Hydroxylation Catalysts.- Benoit Cardinal-David, Karl A. Scheidt: Carbene Catalysis: Beyond the Benzoin and Stetter Reactions.- Kenso Soai and Tsuneomi Kawasaki: Asymmetric autocatalysis of pyrimidyl alkanol.- Douglas C. Behenna and Brian M. Stoltz: Natural Products as Inspiration for Reaction Development: Catalytic Enantioselective Decarboxylative Reactions of Prochiral Enolate Equivalents. Hisashi Yamamoto: Acid Catalysis in Organic Synthesis.

When this book was first conceived as a project the expanding interest in the clinical use of platinum and gold complexes made a survey of the relevant biological properties of metal complexes timely and appropriate. This timeliness has not diminished during the gestation and final publica tion of the manuscript. The introduction contains an explanation of the layout and approach to the book, which I wrote as an overall survey of the wide variety of biological properties of metal complexes. Hopefully, the reader will see the parallels in mechanisms and behavior, even in different organisms. The writing was considerably helped by the enthusiasm and confidence (totally unearned on my part) in the project of Professor Brian James and lowe him my special thanks. I also owe a great debt of gratitude to my colleagues, and especially to Eucler Paniago, of the Universidade Federal de Minas Gerais, for their comprehension and for the initial leave of absence which allowed me to begin the project. To those who read some or all of the manuscript and made suggestions, Bernhard Lippert, Kirsten Skov, and Tom Tritton, as well as the editor's reviewer I am also grateful. As usual, the final responsibility for errors or otherwise rests with the author."

S. Di Bella, C. Dragonetti, M. Pizzotti, D. Roberto, F. Tessore, R. Ugo: Coordination and Organometallic Complexes as Second-Order Nonlinear Optical Molecular Materials.- M. G. Humphrey, M.P. Cifuentes, M. Samoc: NLO Molecules and Materials Based on Organometallics: Cubic NLO Properties.- L. Murphy, J. A. G. Williams: Luminescent Platinum Compounds: From Molecules to OLEDs. - Z. Liu, Z. Bian, C. Huang: Luminescent Iridium Complexes and Their Applications.- N. C. Fletcher, M. C. Lagunas: Chromo- and Fluorogenic Organometallic Sensors.- V. Guerchais, H. Le Bozec: Metal Complexes Featuring Photochromic Ligands.

Metal-Ligand Interactions - Structure and Reactivity emphasizes the experimental determination of structure and dynamics, supported by the theoretical and computational approaches needed to establish the concepts and guide the experiments. Leading experts present masterly surveys of: clusters, inorganic complexes, surfaces, catalysis, ab initio theory, density functional theory, semiempirical methods, and dynamics. Besides the presentations of the fields of study themselves, the papers also bring out those aspects that impinge on, or could benefit from, progress in other disciplines. Refined in the fire of an interactive and stimulating conference, the papers presented here represent the state of the art of current research.

There are only few topics in organometallic chemistry, which have stimulated research activities in as many areas, as transition-metal carbene (alkylidene) complexes. About 25 years after the first planned synthesis of a carbene complex in E.O. Fischer's laboratory in Munich the NATO Advanced Research Workshop on Transition-Metal Carbene Complexes was the first meeting which, brought together scientists from different disciplines to discuss inorganic, organic, theoretical structural catalysis-related aspects of metal carbene chemistry. The 70th birthday of Professor E.O. Fischer was a good occasion for this enterprise. The organizers of the meeting (K.D. Dotz, Marburg; F.R. KreiBl, Munchen; U. Schubert, Wurzburg) were encouraged by the fact that most of the leading scientists in this area were able to participate in the workshop. The very high standard of the contributions is reflected in this book, which contains papers from the majority of the participants. The Proceedings show the state of the art in metal carbene chemistry and will hopefully be a landmark in the development of this area of chemistry. Generous financial support for the workshop and for the preparation of this book was provided by the Scientific Affairs Division of NATO and some companies. The organizers also acknowledge the efforts of the staff of the Bildungs zentrum der Hans-Seidel-Stiftung in Wild bad Kreuth for creating a pleasant and stimulating atmosphere during the conference."

Metal carbene complexes have made their way from organometallic curiosities to valuable reagents and catalysts. They offer novel synthetic opportunities in carbon carbon bond formation based on either carbene-centered reactions or on metal-templated processes which makes them indispensable in modern synthetic methodology. The most prominent metal carbenes are now either commercially available or easy to synthesize and handle by modern laboratory techniques. This volume organized in eight chapters written by the leading scientists in the field illustrates the theoretical background, non-classical nucleophilic and cycloaddition patterns, chromium-templated benzannulation and photo-induced reactions, rhodium-catalyzed carbene transfer as well as the principles and applications of olefin metathesis which coined the progress in synthetic methodology over the past decade. Designed for researchers in academia and industry as well as graduate students it presents the state-of-the-art potential of carbene complexes in modern organic synthesis.

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.

Molecular ruthenium catalysts, during the last decade, have provided new indispensable synthetic methods that cannot be promoted by other catalysts, and they now constitute an emerging field for the selective preparation of fine chemicals. The major reaction types for carbon-carbon and carbon-heteroatom bond formation, most of them with atom economy, are comprehensively discussed by leading experts. The authors highlight the most important discoveries in ruthenium catalysis and propose activation processes, some of them being still controversial. They illustrate the innovation and usefulness in organic synthesis of specific reactions including carbocyclization, cyclopropanation, olefin metathesis, carbonylation, oxidation, transformation of silicon containing substrates, and show novel reactions operating via vinylidene intermediates, radical processes, inert bonds activation as well as catalysis in water. Therefore, the reader will receive a balanced view of this rapidly developing field.

The past decade has seen a dramatic acceleration of activity and interest in phenomena surrounding lanthanide and actinide organo metallic compounds. Around the world, active research in organo-f element synthesis, chemistry, catalysis, crystallography, and quantum chemistry is in progress. This activity has spanned a remarkably wide range of disciplines, from synthetic/mechanistic inorganic and organic chemistry to radiochemistry, catalytic chemistry, spectroscopy (vibra tional, optical, magnetic resonance, photoelectron, Mossbauer), X-ray and neutron diffraction structural analysis, as well as to crystal field and molecular orbital theoretical studies at the interface of chemistry and physics. These investigations have been motivated both by fundamental and applied goals. The evidence that f-element organo metallic compounds have unique chemical and physical properties which cannot be duplicated by organometallic compounds of d-block elements has suggested many new areas of endeavor and application. For these reasons, a great many scientists felt the need for some international forum devoted exclusively to the subject of lanthanide and actinide organometallic compounds. In September of 1978, a NATO Advanced Study Institute entitled, "Organometallics of the f-Elements," was held at the SOGESTA Conference Center near Urbino, Italy. It was the universal feeling of the partic ipants that this first meeting was a great success and that vital international communication and collaboration had been stimulated. The principal lectures at this Institute were published by Reidel in 1979 as part of the NATO ASI Monograph Series ("Organometallics of the f-Elements," T. J. Marks and R. D. Fischer, editors)."

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."

Well tailored metal catalysts are catalysts of the new generation resulting from scientific development at the boundary between homogeneous and hetero- geneous chemistry. The main factors involved in making tailored metal catalysts are not those of traditional impregnation in which the chemistry is in general unknown and ill-defined, or of simple ion exchange which involves long-range forces with little control on the local structure through definite and special bond direction. Tailored Metal Catalysts thus has a rather different emphasis from normal review publications in the field of catalysis. Here we concentrate more on the distinct surface chemistry and catalytic properties of important established materials with well-characterized active structures or precursors, although at the same time providing a systematic presentation of relevant data. Many pioneering works have been undertaken in the field of tailored metal catalysts since the early research on polymer-attached homogeneous metal complexes by the British Petroleum Company Ltd. and the Mobil Oil Corpora- tion around 1969; transition metal complexes attached on polymers by Grubbs (1971), Heinemann (1971), Manassen (1971), Pittman (1971), Bursian et al. (1972), Kagan (1973), Bailar (1974); transition metal complexes attached on inorganic oxides by Allum et al. (1972), Ballard (1973), Candlin and Thomas (1974), Murrell (1974), Yermakov (1974); metal carbonyls/polymers by Moffat (1970); metal carbonyls/inorganic oxides by Parkyns (1965), Davie et al. (1969), Banks et al. (1969), Howe (1973), Burwell (1975); metal carbonyl clusters/ polymers by Colhnan (1972); metal carbonyl clusters/inorganic oxides by Robertson and Webb (1974), Anderson (1974), Smith et al. (1975).

Since the first application of dendrimers in catalysis in the mid 1990s, this field has advanced rapidly. As a consequence, catalytically active dendrimers have emerged as a class of molecular catalysts that has substantially enriched the field of homogeneous (and in part heterogeneous) catalysis. A general survey of transition metal dendrimer catalysts and the way they have developed is followed by in-depth discussions of dendritic transition metal catalysis based on non-covalent catalyst-support interaction and an overview of the rapidly growing field of stereoselective dendrimer catalysis. The development of dendrimer-encapsulated bimetallic nanoparticles has provided the interface with heterogeneous colloid catalysis. As cheaper and readily accessible alternatives to regular dendrimers, hyperbranched polymers are increasingly being used as catalyst platforms. These topics are complemented by a review of metallodendritic exoreptors for the redox recognition of oxo-anions and halides.

TheprototypicalcatalyticreductiveC-Cbondformations,theFischer-Tropsch reaction [1] and alkene hydroformylation [2], were discovered in 1922 and 1938, respectively [3,4]. These processes, which involve reductive coupling to carbon monoxide, have long been applied to the industrial manufacture of commodity chemicals [5]. Notably, alkene hydroformylation, also known as the oxo-synthesis, has emerged as the largest volume application of homo- neous metal catalysis, accounting for the production of over 7 million metric tons of aldehyde annually. Despite the impact of these prototypical reductive C-C bond formations, this ?eld of research lay fallow for several decades. Eventually, the increased availability of mild terminal reductants, in part- ular silanes, led to a renaissance in the area of catalytic reductive C-C bond formation.Forexample,the?rstcatalyticreductiveC-Ccouplingsbeyond- droformylation, which involve the hydrosilylative dimerization of conjugated dienes [6-12], appeared in 1969 - approximately 16 years after the ?rst - ported metal-catalyzed alkene hydrosilylation [13]. Following these seminal studies, the ?eld of catalytic reductive C-C bond formation underwent exp- sivegrowth,culminatingintheemergenceofanevergrowingbodyofresearch encompassing a powerful set of transformations. To our knowledge, no thematic volumes devoted solely to metal-catalyzed reductive C-C bond formationhave been assembled. For the ?rst time, in this issue of Topics in Current Chemistry,wepresent acompilation ofmonographs from several leaders in this burgeoning area of research. This collection of reviews serves to capture the diversity of catalytic reductive C-C couplings presently available and, in turn, the remarkable range of reactivity embodied by such transformations. There is no indication that this ?eld has reached its zenithanditisthehopeofthepresentauthorthatthisvolumewillfuelfurther progress.