The revolutionary impetus of the NMR methods in organic chemistry has parallels in the field of boron chemistry. lIB NMR spectroscopy provided a basis for the elucida tion of structures and reactions of the boron hydrides. However, although many studies have been carried out with the higher boranes, carboranes, metalloboranes, etc., and although certain patterns have emerged, the correlation between the observed chemical shift and the assigned structural unit is still not fully understood. Therefore, predictions in this area are still rather limited, and semiquantitative interpretations are not yet pos sible. Several years ago Eaton and Lipscomb sUpImarized the status in this field in their book "NMR Studies of Boron Hydrides and Related Compounds" and a plethora of new data has accumulated since then. The book also contained material on simple bo rane derivatives, but they were not discussed in any detail. On the other hand many systematic studies, both synthetic and spectroscopic, have been conducted on these simple boron materials in the last decade. Thus a large amount of NMR information is available, not only on lIB but also on 1 H, 1 3 C, and 14 N. However, this information is widely scattered in the literature, and often the data are not discussed at all. It see med appropriate, therefore, to collect these data and to present them in one volume."

New methods for the determination of the nature, proportion, and distribution of structural defects in microcrystallized lamellar systems are of utmost importance not only to experimentalists but also to theoreticians. Mathematical formalism - indispensable for such analyses - is well-illustrated by various examples, allowing this method to be easily adopted and even to be applied to other solids with lamellar or pseudo-lamellar structures.

The field of Physical Chemistry has developed through the application of theories and concepts developed by physicists to properties or processes of interest to chemists. Physicists, being principally concerned with the basic ideas, have generally restricted their attention to the simplest systems to which the concepts applied, and the task of applying the techniques and theories to the myriad substances and processes that comprise chemistry has been that of the physical chemists. The field of Solid State Chemistry has developed with a major impetus from the synthetic chemists who prepared unusual, novel materials with the principal guid ing ideas growing out of an understanding of crystal structure and crystal structure relationships. The novel materials that pour forth from this chemical cornucopia cry out for further characterization and interpretation. The major techniques for the characterization and interpretation of crystalline solids have been developed in the fields of Solid State Physics and Crystallography. Thus, the need arose for expanding the realm of Physical Chemistry from its traditional concern with molecules and their properties and reactions to include the physics and chemistry of crystalline solids. This book deals with the applications of crystallography, group theory and thermodynamics to problems dealing with non molecular crystalline solids."

Solid-State NMR is a branch of Nuclear Magnetic Resonance which is presently experiencing a phase of strongly increasing popularity. The most striking evidence is the large number of contributions from Solid-State Resonance at NMR meetings, approaching that ofliquid state resonance. Important progress can be observed in the areas of methodological developments and applications to organic and inorganic matter. One volume devoted to more or less one of each of these areas has been published in the preceding three issues. This volume can be considered an addendum to this series. Selected methods and applications of Solid-State NMR are featured in three chapters. The first one treats the recoupling of dipolar interactions in solids, which are averaged by fast sample rotation. Following an introduction to effective Hamiltonians and Floquet theory, different types of experiment such as rotary resonance, dipolar chemical shift correlation spectroscopy, rotational resonance and multipulse recoupling are treated in the powerful Floquet formalism. In the second chapter, the different approaches to line narrowing of quadrupolar nuclei are reviewed in a. consistent formulation of double resonance (DaR) and dynamic angle spinning (DAS). Practical aspects of probe design are considered as well as advanced 2D experiments, sensitivity enhancement techniques, and spinning sideband manipulations. The use of such techniques dramatically increases the number of nuclei which can be probed in high resolution NMR spectroscopy. The final chapter describes new experimental approaches and results of structural studies of noncrystalline solids."

1. A.-R. Grimmer, Berlin, FRG; B. Bl}mich, Aachen, FRG: Introduction to Solid-State NMR 2. F. Laupretre, Paris, France: High-Resolution 13C NMRInvestigations of Local Dynamics in Bulk Polymers at Temperatures Below andAbove the Glass-Transition Temperature 3. D. Raftery, Philadelphia, PA;B.F. Chmelka, Santa Barbara, CA: Xenon NMR Spectroscopy 4. G. Fleischer, Leipzig, FRG; F. Fujara, Mainz, FRG: NMR as a Generalized Incoherent Scattering Experiment 5. P. Bl}mler, B. Bl}mich, Mainz, FRG: NMR Imaging of Solids

New Trends in Enzyme Catalysis and Biomimetic Chemical Reactions embraces modern areas of enzyme catalysis where other books in the field concentrate mainly on kinetic, bioorganic and biochemical aspects of the enzyme catalysis and do not cover biophysical and physicochemical problems. Topics covered include:

-modern physical and kinetic methods of investigation,
-contemporary theories of elementary chemical processes in enzymes,
-structure, dynamics and action mechanism of enzyme active sites,
-concept of pretransition state,
-theory of long-range electron transfer and proton translocation,
-mechanisms of "tough" biochemical reactions (dinitrogen reduction, light energy conversation, water photooxidation, hydroxilation),
-the achievements and problems of biomimetic chemical reactions.

Assembling a program in bioinorganic chemistry that is scientifi cally relevant, well defined, and self-consistent is not an easy task. In this attempt we decided to consider zinc enzymes, copper oxidases, cytochromes and cytochrome oxidase. The choice is in part due to the great attention that the current specialized literature devotes to these topics, which are now debated among chemists, biochemists, biophysicists, etc .. We believe that hydration reactions, hydrolytic and oxidative processes have much in common from the point of view of the reaction mechanisms, the comprehension of which represents a frontier of science. For these reasons these topics have been the subject of the NATO-ASI held at San Miniato, Pisa, Italy, from May 28 to June 8, 1982. We hope we can transfer here the main conclusions of what (we believe) was a very stimulating scientific meeting. We would like to thank the local saving bank, Cassa di Risparmio di San Miniato, for helping in many ways. The financial contribution from the European Research Office of the US Army, and from the Bruker Spectrospin s.r.l., Italy, is also acknowledged. The National Science Foundation of the United States has provided a travel grant to one of the participants from the U.S.A. We are grateful to the NATO Scientific Affairs Division which provided a grant to finance this Institute."

"Modern Crystallography IV" is devoted to a systematic and up- to-date description of fundamental physical properties of solid and liquid crystals. These include elastic and mechanical, dielectric and ferroelectric, magnetic and optical properties, transport phenomena and spectroscopy. An important feature of the treatment is its use of the crystallographic approach, an introduction to which is given in the opening chapter of the book. The topics are treated at a level understandable to students who have two years of university physics. Researchers and engineers working on practical applications should also find the book useful, as should specialists in other fields who wish to broaden their knowledge of crystallography and materials science. The book is written by a group of leading scientists from the Institute of Crystallography of the USSR Academy of Sciences.

Early in this century, the newly discovered x-ray diffraction by crystals made a complete change in crystallography and in the whole science of the atomic structure of matter, thus giving a new impetus to the development of solid-state physics. Crystallographic methods, pri marily x-ray diffraction analysis, penetrated into materials sciences, mol ecular physics, and chemistry, and also into many other branches of science. Later, electron and neutron diffraction structure analyses be came important since they not only complement x-ray data, but also supply new information on the atomic and the real structure of crystals. Electron microscopy and other modern methods of investigating mat ter-optical, electronic paramagnetic, nuclear magnetic, and other res onance techniques-yield a large amount of information on the atomic, electronic, and real crystal structures. Crystal physics has also undergone vigorous development. Many re markable phenomena have been discovered in crystals and then found various practical applications. Other important factors promoting the development of crystallog raphy were the elaboration of the theory of crystal growth (which brought crystallography closer to thermodynamics and physical chem istry) and the development of the various methods of growing synthetic crystals dictated by practical needs. Man-made crystals became increas ingly important for physical investigations, and they rapidly invaded technology. The production . of synthetic crystals made a tremendous impact on the traditional branches: the mechanical treatment of mate rials, precision instrument making, and the jewelry industry."

Clusters of Atoms and Molecules I is devoted to theoretical concepts and experimental techniques important in the rapidly expanding field of cluster science. Cluster properties are dicussed for clusters composed of alkali metals, semiconductors, transition metals, carbon, oxides and halides of alkali metals, rare gases, and neutral molecules. The book contains several well-integrated treatments, all prepared by experts. Each contribution starts out as simple as possible and ends with the latest results, so that the book can serve as a text for a course, an introduction into the field, or as a reference book for the expert.

This volume represents an edited selection of papers presented at the International symposium on the geology of tin deposits held in Nanning City in October 1984. It documents a great advance in our knowledge of tin deposits, particularly of the People's Republic of China. Details are presented in English for the first time on the major tin-polymetallic sulphide deposits of Dachang and Gejiu, which bear similarities to the deposits of Tasmania, but are little known to the geological community outside of China. The publication of this volume was sponsored by the United Nations ESCAP Regional Mineral Resources Development Centre (RMRDC), now a Regional Mineral Resources Development Project (RMRDP) within ESCAP. The Centre had previously published a report on the Symposium in Nanning City and the following field trip to the Dachang tin-polymetallic sulphide deposit of Guangxi, entitled "Report on the International Symposium on the Geology of Tin Deposits: Nanning and Dachang, China, 27 October - 8 November 1984." It is my privilege to acknowledge the help provided by Dr. J. F. McDivitt and Dr. H. W. Gebert, co-ordinator of ESCAP-RMRDC.

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).

In the last two decades low-dimensional (low-d) physics has matured into a major branch of science. Quite generally we may define a system with restricted dimensionality d as an object that is infinite only in one or two spatial directions (d = 1 and 2). Such a definition comprises isolated single chains or layers, but also fibres and thin layers (films) of varying but finite thickness. Clearly, a multitude of physical phenomena, notably in solid state physics, fall into these categories. As examples, we may mention: * Magnetic chains or layers (thin-film technology). * Metallic films (homogeneous or heterogeneous, crystalline, amorphous or microcristalline, etc.). * I-d or 2-d conductors and superconductors. * Intercalated systems. * 2-d electron gases (electrons on helium, semiconductor interfaces). * Surface layer problems (2-d melting of monolayers of noble gases on a substrate, surface problems in general). * Superfluid films of ~He or 'He. * Polymer physics. * Organic and inorganic chain conductors, superionic conductors. * I-d or 2-d molecular crystals and liquid crystals. * I-d or 2-d ferro- and antiferro electrics.

This, the second and final volume of Reactions of Coordinated Ligands, describes the chemistry of ligands bound through non-carbon atoms, and of coordinated carbon dioxide. As before, emphasis is on the underlying mechanisms, which provide a unity of understanding for superficially disparate processes. The wide range of topics covered illustrates well both the versatility and the usefulness of coordination chemistry in the controlled activation of ligands. Looking to the future, carbon dioxide is the feedstock of last resort. The homogeneous reduction of dinitrogen to ammonia now seems unlikely to replace the Haber process, but solution reactions also lead to more complex, varied, and valuable products. Nitrogen monoxide, a "non innocent" ligand, impinges as pollutant and reagent. Its rich chemistry stems from its linked roles as three-electron donor, and as extremely powerful -acceptor. In the hydrolysis and condensation of complexed amides, esters etc., metals act both as templates and as tunable and poly functional Lewis acids. Here the control of hydrophobic and steric interactions begins to model the subtle mechanisms of biological specificity. Finally, phosphorus and sulfur are imporant both as ligand atoms in themselves, and as anchors for other functionalities. I would like to thank all those who have been involved in the writing and production of this work, and also my colleagues old and new, at Glasgow and the University of North Texas, for their support. Paul S. Braterman v CONTENTS 1. Reactions of Coordinated Carbon Dioxide 1 J. D. Miller 1."

Chromium oxidation, well known and widely explored in organic chemistry since the very beginning of this science, is a topic of current interest for the organic chemist as evidenced by the continuous development of new techni ques and procedures reported in the literature. Chromium oxidation is a simple process which can be easily performed in the laboratory and scaled up in industry as well. Although almost every oxidizable organic functional group may undergo chromium oxidation, the most important fields of appli cation are the oxidation of alcohols, allylic and benzylic oxidation, oxidative degradation and oxidation of some organometallic compounds. A high degree of selectivity is often possible by choosing the most suitable reagent among those several ones now available. This book takes account of the various functional groups that undergo oxidation and the entire literature up to 1982. It has been written in the hope to help the synthetic organic chemist in his experimental work. For this purpose a number of tables comprising yields and references have been included; detailed descriptions of typical procedures are meant to show the experimental conditions and the scope of the reactions. We wish to thank Dr. Mario Orena for his valuable scientific and technical assistence and Prof. Bruno Camerino, who read the entire manuscript and corrected many of the errors. Bologna, February 1984 Gianfranco Cainelli Giuliana Cardillo Table of Contents I. Introduction . . . . . . . . . . ."

Glass Chemistry is concerned with the relation of chemical composition, structure and properties of various glasses. The book has been translated from the third German edition, which serves as a textbook for university students in materials sciences and a reference book for scientists and engineers in glass science and production. The central themes of the book are the chemistry and physics of glass. Detailed knowledge of the compositional and structural facts is the basis for the systematic development of new glasses as construction and optical materials.
Glass Chemistry is an interdisciplinary book on the borderlines between chemistry, physics, mineralogy and even biology and medicine. The book represents a well balanced treatment for students, scientists and engineers.

The literature on the geology, chemistry, and biochemistry of phosphorus generally takes its mineralogy for granted. The in cidental information on phosphate minerals given in these texts is often obsolescent and inaccurate. The few mineralogical texts that have dealt comprehensively with the phosphate minerals have now become outdated, and typically present the essential information in a manner unsuitable for nongeological readers. This volume is intended as a ready reference for workers who require good basic information on phosphate minerals or their synthetic equivalents. The topics covered should appeal to geologists and geochemists, lithologists, environmental scientists and engineers, chemists and biochemists who have any interest in the intricate world of phosphorus. The hard tissues of many vertebrates and the many pathological calcifications consist mostly of phosphate minerals. The precipita tion of these compounds also plays a major role in the ecological cycling of phosphorus, and occasionally even dominates the behavior of many trace metals in many geochemical and biolog ical systems. Indeed, many pegmatitic phosphate minerals have acquired some notoriety because of the rarer trace metals which they tend to accumulate. With the commercialization of phosphate fertilizers since the early part of the 19th century, phosphate minerals have assumed an important role in industrial chemistry and agriculture. Clearly, the study of phosphate minerals is important from the economic, agricultural, environmental and (human and animal) health viewpoint."

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 primary literature on organometallic chemistry has undergone phenomenal growth. The number of papers published from 1951 to 1976 is about equal to all prior literature. Together with this intense activity there has developed a complexity in the literature. Thus, specialized texts and teaching texts, a review journal, an advanced series, and a research journal have all appeared during this period. The present series also reflects this growth and recognizes that many categories of organometallic compounds now have numerous representatives in the literature. The purpose of Organometallic Reactions and Syntheses is to provide complete chapters on selected categories of organometallic compounds, describing the methods by which they have been synthesized and the reactions they undergo. The emphasis is on the experimental aspects, although struc tures of compounds and mechanisms of reactions are discussed briefly and referenced. Tables of all of the compounds prepared in the category under consideration and detailed directions for specific types make these chapters particularly helpful to the preparative chemist. While the specific directions have not been referenced in the same way. as are those in Organic Syntheses and Inorganic Syntheses, the personal experiences of the authors often lend special merit to the procedures and enable the reader to avoid many of the pitfalls frequently encountered in selecting an experimental procedure from the literature."

The nitrides and carbides of boron and silicon are proving to be an excellent choice when selecting materials for the design of devices that are to be employed under particularly demanding environmental and thermal con- tions. The high degree of cross-linking, due to the preferred coordination numbers of the predominantly covalently bonded constituents equalling or exceeding three, lends these non-oxidic ceramics a high kinetic stability, and is regarded as the microscopic origin of their impressive thermal and mechanical durability. Thus it does not come as a surprise that the chemistry, the physical properties and the engineering of the corresponding binary, ternary, and even quaternary compounds have been the subject of intensive and sustained efforts in research and development. In the five reviews presented in the volumes 101 and 102 of "Structure and Bonding" an attempt has been made to cover both the essential and the most recent advances achieved in this particular field of materials research. The scope of the individual contributions is such as to address both graduate students, specializing in ceramic materials, and all scientists in academia or industry dealing with materials research and development. Each review provides, in its introductory part, the chemical, physical and, to some extent, historical background of the respective material, and then focuses on the most relevant and the most recent achievements.

Springer-Verlag, Berlin Heidelberg, in conjunction with Springer-Verlag New York, is pleased to announce a new series: CRYSTALS Growth, Properties, and Applications The series presents critical reviews of recent developments in the field of crystal growth, properties, and applications. A substantial portion of the new series will be devoted to the theory, mechanisms, and techniques of crystal growth. Occasionally, clear, concise, complete, and tested instructions for growing crystals will be published, particularly in the case of methods and procedures that promise to have general applicability. Responding to the ever-increasing need for crystal substances in research and industry, appropriate space will be devoted to methods of crystal characterization and analysis in the broadest sense, even though reproducible results may be expected only when structures, microstructures, and composition are really known. Relations among procedures, properties, and the morphology of crystals will also be treated with reference to specific aspects of their practical application. In this way the series will bridge the gaps between the needs of research and industry, the pos sibilities and limitations of crystal growth, and the properties of crystals. Reports on the broad spectrum of new applications - in electronics, laser tech nology, and nonlinear optics, to name only a few - will be of interest not only to industry and technology, but to wider areas of applied physics as well and to solid state physics in particular. In response to the growing interest in and importance of organic crystals and polymers, they will also be treated."

The nitrides and carbides of boron and silicon are proving to be an excellent choice when selecting materials for the design of devices that are to be employed under particularly demanding environmental and thermal con- tions. The high degree of cross-linking, due to the preferred coordination numbers of the predominantly covalently bonded constituents equalling or exceeding three, lends these non-oxidic ceramics a high kinetic stability, and is regarded as the microscopic origin of their impressive thermal and mechanical durability. Thus it does not come as a surprise that the chemistry, the physical properties and the engineering of the corresponding binary, ternary, and even quaternary compounds have been the subject of intensive and sustained efforts in research and development. In the five reviews presented in the volumes 101 and 102 of "Structure and Bonding" an attempt has been made to cover both the essential and the most recent advances achieved in this particular field of materials research. The scope of the individual contributions is such as to address both graduate students, specializing in ceramic materials, and all scientists in academia or industry dealing with materials research and development. Each review provides, in its introductory part, the chemical, physical and, to some extent, historical background of the respective material, and then focuses on the most relevant and the most recent achievements.

This book is aimed at graduate students and research workers in aU branches of ohemistry, who wish to gain insight into what continues'to be one of the fastest growing areas of the subject. Aonding to a metal center may stabilize a ligand towards some reagents, activate it towards others, or modify its chemical behavior in more subtle ways. AU these effects have their uses, and aU invite understanding in terms of mechanism. Thus mechanistic insight is linked to control of reaction pathways. The detailed working out of this relationship provides the central theme of the book. The effect of the metal may be electronic or steric, and may involve the energy or the entropy of activation. It may depend on changes induced in the initial state of the ligand, or on those that only arise further along the reaction pathway. It may involve one coordination site or several, and the effects may be more, or less, specific to the metal involved and more, or less, amenable to control through the other Jigands. These remarks apply equaUy strongly to the carbon-bound ligands which occupy the major part of this work, and to those attached by other atoms. Thus the reactions discussed here are relevant in such diverse areas as bulk homogeneous catalysis, stereoselective stoichiometric synthesis, and bioinorganic chemistry.

Chemical Synthesis: Gnosis to Prognosis (XTUllKtl ~uv8eoTr ana TT) rVWOT) OTT) npaYVWOT)) " . . . . other things being equal, that field has the most merit which contributes most heavily to, and illuminates most brightly, its neighbouring scientific disciplines[l] One hundred scientists, a blend of students, industrialists, and academics from twenty countries gathered to circumscribe, understand, and elaborate this topic in the magical setting of Ravello, Italy. The mandate of this workshop? To survey existing knowledge, assess current work, and discuss the future directions of chemical synthesis as it impinges on three exciting interdisciplinary themes of science in the 1990's: bioactive molecules, man-made chemical materials, and molecular recognition. This tempting but inexact menu summoned diverse students and scientists who wished to seriously reflect upon, dissect, and eject ideas and own experiences into open debate on this topic, which is at a crossroad in internal evolution and impact on the life and material sciences. The group arrived from many directions and in various forms of transportation, matters soon forgotten, when it found itself in the village which nurtured Wagner's inspiration and set to work immediately to ponder the question which has received extensive thought, prediction, and caveat from illustrious chemists over a period of time [2], two of which, to the delight of all, in presence among the Lectures.

Walter C. J. ROSS Emeritus Professor, University of London To paraphrase a statement made by Howard E. Skipper many years ago, 'We cancer chemotherapists have often exploited and overworked our chemist colleagues and they have been conveniently forgotten at award giving times'. This book is an attempt to rectify this and highlight the contribution of the chemist in modifying the structure of various types of agent to enhance their effectiveness as inhibitors of the growth of neoplastic tissues. Cancer chemotherapy is a relatively new discipline, coming later than the introduction of sulphonamides and antibiotics. Modern anti-cancer therapy started with the report of the use of a war gas methyl-di-(2-chloroethyl)amine (HN2) in 1946 for the treatment of Hodgkin's disease. The recognition that this compound acted as a bifunctional alkylating agent under physiological conditions led to the synthesis of a wide range of drugs with similar properties. Amongst these were chlorambucil, melphalan, busulphan, and cyclophos phamide which still find use today. Somewhat later, a range of antibiotics was found to be effective, for example aminopterin (1948) and 6-mercaptopurine (1958) to treat acute leukaemias and 5-fluorouracil and 6-azauracil (1957-8) which were used against a variety of cancers. Since these early days the net has been cast ever wider and, as well as ingenious modifications of the compounds mentioned above, anticancer drugs now include growing classes of compounds ranging from purely synthetic agents to natural products. Many of these are discussed in the present book."