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Books > Science & Mathematics > Chemistry > Inorganic chemistry > General
The success of the first edition of this book has encouraged us to revise and update it. In the second edition we have attempted to further clarify por tions of the text in reference to point symmetry, keeping certain sections and removing others. The ever-expanding interest in solids necessitates some discussion on space symmetry. In this edition we have expanded the discus sion on point symmetry to include space symmetry. The selection rules in clude space group selection rules (for k = 0). Numerous examples are pro vided to acquaint the reader with the procedure necessary to accomplish this. Recent examples from the literature are given to illustrate the use of group theory in the interpretation of molecular spectra and in the determination of molecular structure. The text is intended for scientists and students with only a limited theoretical background in spectroscopy. For this reason we have presented detailed procedures for carrying out the selection rules and normal coor dinate treatment of molecules. We have chosen to exclude discussion on symmetry aspects of molecular orbital theory and ligand field theory. It has been our approach to highlight vibrational data only, primarily to keep the size and cost of the book to a reasonable limit."
Zaozao Qiu shows in this thesis that transition metals can mediate or catalyze the cycloaddition or coupling reactions of carboryne with alkynes or alkenes to afford benzocarboranes, alkenylcarboranes or dihydrobenzocarboranes. These results represent powerful strategies to assemble useful complex molecules from very simple precursors in a single operation. Carboranes have many applications in medicine. However, their unique structures make derivatization difficult and the limited efficient synthetic methods to obtain functional carborane materials have restricted applications of carboranes within a narrow scope. This work breaks a new ground in metal-carboryne chemistry and will have a significant impact on synthetic, cluster and materials chemistry.
One of the major challenges of science in the last few years of the second millennium is learning how to design materials which can fulfill specific tasks. Ambitious as it may be, the possibilities of success are not ne li ble provided that all the different expertises merge to overcome the limits of eXIsting disciplines and forming new paradigms science. The NATO Advanced Research Workshop on "Magnetic Molecular Materials" was organized with the above considerations in mind in order to determine which are the most appropriate synthetic strategies, experimental techniques of investigation, and theoretical models which are needed in order to develop new classes of magnetic materials which are based on molecules rather than on metallic or ionic lattices. Why molecules? The answer may be obvious: molecular chemistry in principle fine can tune the structures and the properties of complex aggregates, and nature already provides a large number of molecular aggregates which can perform the most disparate functions. The contributions collected in this book provide a rather complete view of the current research accomplishments of magnetic molecular materials. There are several different synthetic approaches which are followed ranging from purely organic to inorganic materials. Some encouraging successes have already been achieved, even if the critical temperatures below which magnetic order is observed still are in the range requiring liquid helium.
1 Oxford and Webster's dictionaries,2 give trans-Atlantic agreement in English with a common definition for 'Quality' as 'degree of excellence'. Compared with the many words taken up by other authors' definitions, this is remarkably brief and no doubt unsatisfactory to many people. Yet if 'degree' means a stage in an ascending or descending series, in intensity or in amount, then measurement is by definition explicitly required if terms such as 'quality level', 'good quality', 'high quality' etc. are to have any real meaning. Using measurement is inherent in the methods of all the major writers on the achievement of business improvement through quality. Results from measurements allow improvement by using tools commonly grouped under the heading Statistical Process Control (SPC). Results also form part of the judging criteria of Total Quality Management (TQM) models such as the Malcolm Baldrige National Quality Award in the USA and the more recent European Quality Award. Future revisions of the ISO 9000 series of quality management system standards will specifically require measure ment of defects. However, it is not easy for quality professionals or line managers to find examples of what they should measure and how to do it in their own particular functions in their own particular industries; case st\}dies always seem to refer to others."
This volume contains the proceedings of the NATO Advanced Research Workshop on "Atomic and Molecular Wires". It was sponsored by the Ministry of Scientific Affairs Division special program on Nanoscale Science with the support of the CNRS and the Max Planck Institute. Scientists working or interested in the properties of wires at a subnanoscale were brought together in Les Houches (France) from 6 to 10 May 1996. Subnanoscale wires can be fabricated either by surface physicists (atomic wires) or by synthetic chemists (molecular wires). Both communities present their foremost advances using, for example, STM to assemble atomic lines atom for atom, to fabricate a mask for such a line or using the wide range of chemical synthesis techniques to obtain long, rigid and conjugated oligomers. Interconnecting such tiny wires to sources (voltage, current) continues to demand a great technological effort. But nanolithography associated with microfabrication or STM are now clearly identified paths for measuring the electrical resistance of an atomic or a molecular wire. The first measurements have been reported on Xe , benzene, C ' di(phenylene-ethynylene) showing 2 60 the need for a deeper understanding of transport phenomena through subnanowires. Such transport phenomena like tunnel (off-resonance) transport and Coulomb blockade have been discussed by theorists with an emphasis on the exponential decrease of the tunnel current with the wire length versus the ballistic regime of transport.
This book introduces the concept of crystallographic non- rigidity and asymmetry of the transition elements as central atoms organometallic compounds. This intrinsic behavior of central atoms in condensed matter is quantified by applying statistical approach. Averaging of extrinsic factors in crystal structures is tested by using variance analysis. Introductionof the above mentioned concept and applications of variance analysis as an approximation for considering factors influencing properties of central atomin the crystal is original and new.
Nearly three years have passed since the publication of the original Russian edition, in which time there have appeared various papers on recent research on the transuranium elements, of which the most notable concern the production of element 105 at Dubna and Berkeley. There has also been much fresh information on elements 104 (kurchatovium) and 103 (lawrencium). Our knowledge of shell effects in the fission barrier has been extended. Hopes of finding relatively stable superheavy elements have stimulated searches for such elements in nature as well as rapid development in heavy ion acceleration. We may see some very considerable discoveries in the next few years. The new results vary in reliability, and so it is not surprising that some papers on the properties of the heaviest elements have given rise to vigorous debates, whose value lies in the way they ad vance the subject. We have not attempted to give an exhaustive survey of recent papers and have merely added brief sections to reflect what we con sider to be the most important points from these. So far, the United states and the USSR have made the most considerable contributions to the synthesis, study, and use of the transuranium elements, so it is especially welcome to us that this book, first published in our country, should now appear in the USA in an English translation.
The ever-increasing importance of chemical reactions at high and superhigh temperatures in crystalline, amorphous, and semicrystalline SOlids, as well as the reactions of these solids with gases, prompted the authors of this book to examine critically the literature available in this field and to present a general review of the subject. In this monograph we discuss those chemical and physicochemical points which we consider to be most important for solving a series of problems in the preparation and use of new inorganic materials. We hope that this book will be of interest to the many specialists working on inorganic materials. N. A. Toropov PREFACE Modem technology demands ever more materials with high mechanical strength, heat and chemical re sistance, fire resistance, special electrical properties, particular behavior toward active radiations, etc. The search for such materials requires the study of various chemical compounds, metallic alloys, and other fused in organic systems, especially oxide systems. Materials based on oxides begin to assume increasing importance in many fields of the new technology. In this connection the investigation of oxides and systems consisting of two and more oxides is expanding greatly.
During the last decade there has been a renewed interest in under standing from a fundamental point of view the gasification of carbon. Basi cally there are two major issues in controlling the reactivity of carbon: i) reduction of the gasification rate of carbon materials in hostile environment ii) increase of the gasification rate in order to utilize carbonaceous compounds more effectively. Although these two objectives look somewhat contradictory, they are part of the general topics of understanding gasification reactivity of carbon. Refractory applications of carbon in furnace linings, seals and vanes, as well as the use of carbon-carbon or carbon-ceramic composites in struc tures able to withstand corrosion at high temperature require a better understanding of the fundamentals involved in carbon-oxidizing gas (02' CO, H 0) reactions. Furthermore a great interest of aluminium producers 2 2 is 10 extending the lifetime of carbon electrodes in alumina electrolysis which primarily depends on reducing their consumption rates by air or carbon dioxide. Proper control of gasification reactions is also of prime importance in manufacturing carbonaceous adsorbents like granular activated carbon clothes of high adsorption characteristics. The balance between increase of porosity and decrease in mechanical strength during activation is critical for developing new porous types of carbon materials in particular for carbon clothes and this can only be achieved by a careful control of the gasification reaction."
Within the last few years, iron research has yielded exciting new insights into the under standing of normal iron homeostasis. However, normal iron physiology offers little protec tion from the toxic effects of pathological iron accumulation, because nature did not equip us with effective mechanisms of iron excretion. Excess iron may be effectively removed by phlebotomy in hereditary hemochromatosis, but this method cannot be applied to chronic anemias associated with iron overload. In these diseases, iron chelating therapy is the only method available for preventing early death caused mainly by myocardial and hepatic iron toxicity. Iron chelating therapy has changed the quality of life and life expectancy of thalassemic patients. However, the high cost and rigorous requirements of deferoxamine therapy, and the significant toxicity of deferiprone underline the need for the continued development of new and improved orally effective iron chelators. Such development, and the evolution of improved strategies of iron chelating therapy require better understanding of the pathophysiology of iron toxicity and the mechanism of action of iron chelating drugs. The timeliness of the present volume is underlined by several significant develop ments in recent years. New insights have been gained into the molecular basis of aberrant iron handling in hereditary disorders and the pathophysiology of iron overload (Chapters 1-5)."
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.
This series, Mechanisms of Inorganic and Organometallic Reactions, provides an ongoing critical review of the published literature concerned with the mechanisms of reactions of inorganic and organometallic compounds. Emphasis is on reactions in solution, although solid state and gas phase studies are included where they provide mechanistic insight. The sixth volume deals with papers published during the period January 1987 through June 1988 inclusive, together with some earlier work where it is appropriate to make comparisons. Coverage spans the whole area as comprehensively as practically possible, and the cited references are chosen for their relevance to the elucidation of reaction mechanisms. The now familiar format of earlier volumes has been maintained to facilitate tracing progress in a particular topic over several volumes, but some small changes have been made. Reflecting the a'mount of mechanistic work associated with ligand reactivity, and the growing importance of this area, Chapter 12 has been renamed and enlarged to bring together informa tion on both coordination and organometallic systems involving ligand reactions. Numerical data are usually reported in the units used by the original authors, except when making comparisons and conversion to common units is necessary.
In common with the editor of the first edition, my own personal involvement with tin chemistry began when I had the privilege of studying for a PhD degree under the supervision of Professor Alwyn G. Davies FRS at University College London (UCL) almost exactly 30 years ago. Then, following 21 years' service with the International Tin Research Institute, it was a great pleasure for me when the wheel turned full circle and, in 1994, Alwyn - now an Emeritus Professor - asked me to return to UCL as an Honorary Research Fellow in the Chemistry Department. One of my first tasks was when I received an invitation from Blackie A&P to edit the second edition of the Chemistry of Tin, which I was delighted to accept, since it enabled me to continued my life-long interest in tin chemistry and to maintain contact with my former friends and colleagues, many of whom have contributed to this book.
Starting at the dawn of science, History of Industrial Gases traces the development of gas theory from its Aristotelian roots to its modern achievements as a global industry. Dr. Almqvist explores how environmental protection, geographical areas, and the drive for higher purity and efficiency affected development in the nineteenth and twentieth centuries, and how they will influence the future of this rapidly expanding industry. The roles of major contributing companies are also discussed to provide an informative and thought-provoking treatise valuable to anyone who studies or works in this fascinating field.
of Polymer Chemistry, Inc. of the American Chemical Society held its The Division 15th Biennial Polymer Symposium on the topic, "Advances in New Materials," November 17-21, 1990, at the Pier 66 Resort and Marina in Ft. Lauderdale, Florida. A three and one half day program was presented by recognized leaders in major areas of new polymeric materials. The topics of the Biennial Symposium included new high performance polymers, polymers for electronic applications, electrically conducting polymers, nonlinear optics, new polymer systems, and polymers derived from biological media. These are the subject areas of this volume of "Contemporary Topics in Polymer Science." The intent of the Symposium was to focus on recent advances in polymeric materials. The technical sessions were complemented by an initial poster session which augmented the various technical sessions. A particular highlight of the meeting was the presentation to Professor Michael Szwarc of the 1990 Division of Polymer Chemistry Award by Dr. J. L. Benham, Chairman of the T Aymer Division. During his Award address, Professor Szwarc described how he had become a polymer chemist and later developed "living polymers." Without a doubt, Professor Szwarc has made a profound contribution to the polymer field, which has yielded many new forms of living polymerization."
This is a book on one of the most fascinating and controversial areas in contemporary science of carbon, chemistry, and materials science. It concisely summarizes the state of the art in topical and critical reviews written by professionals in this and related fields.
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."
Only in the past decade, has the scientific and industrial community come to realize the potential utility offered by inorganic and organometallic polymers (lOPs) for a wide variety of applications. This potential is especially important for applications requiring multifunctional polymers, e.g. for smart materials, nanotechnology, biomimetic systems (neural networks), photonics, etc; lOPs with special properties. The breadth of perfor- mance requirements for the individual areas of application is enormous as are the problems pertaining to generating low cost, high performance, processable lOPs. This book represents the third in a series of books we have edited on inorganic and organometallic polymer chemistry (1. Transfonnation of Organometallics into Common and Exotic Materials, NATO ASI Series Vol 141. 2. Inorganic and Organometallic Oligo- mers and Polymers, Kluwer publications). In this series, we have attempted to identify important trends that help to define for the reader; the potential scope of lOP science as well as the problems that must be surmounted to realize this potential. The focus of the work presented in the following chapters is primarily on the relationships between lOPs and solid state materials with special properties, e.g. conducting, magnetic, photonic and structural materials.
Distinct scientific communities are usually involved in the three fields of quasi-crystals, of liquid crystals, and of systems having modulated crystalline structures. However, in recent years, there has been a growing feeling that a number of common problems were encountered in the three fields. These comprise the need to recur to "exotic" spaces for describing the type of order of the atomic or molecular configurations of these systems (Euclidian "superspaces" of dimensions greater than 3, or 4-dimensional curved spaces); the recognition that one has to deal with geometrically frustrated systems, and also the occurence of specific excitations (static or dynamic) resulting from the continuous degeneracies of the stable structures considered. In the view of discussing these problems, aNA TO-Advance Research Workshop has assembled in Preveza (Greece), in september 1989,50 experts of the three considered fields (with an equal proportion of theorists and experimentalists). 35 hours of conferences and discussions have led to a more detailed evaluation of the similarities and of the differences in the approaches implemented in the studies of the three types of systems. The papers contained in this NATO-series book provide the substance of this workshop. The reader will find three types of papers. Some very short papers giving the main ideas stated on a subject. Papers comprising 8-10 pages which stick closely to the contents of the talks presented. Longer papers providing more extensively the background and results relative to a given topic. It is worth summarizing the principal outputs of the workshop.
"Nanotechnology" is now very well known as one of the most important key technologies in science and industry. In the field of material science and engineering, nanoparticles should be unit materials, as well as atoms and molecules, to build ceramics, devices, catalysts, and machines, and the "nanoparticle technology" is thus attracting. This novel technology includes various methodologies for nanoparticles: preparation, surface-modification via chemical and/or physical treatments, immobilization and arrangement on supports or substrates, to achieve high performance for luminescence properties in light emitting devices, and high efficiency for catalytic and photocatalytic reactions in chemical synthesis, chemical decomposition, and artificial photosynthesis, etc. It should be needless to say that the preparation of nanoparticles, having precisely controlled particle size, size distribution, chemical composition, and surface properties, is essentially important to realize "true nanoparticle technology". This book, written by Dr. Dibyendu Ganguli and Dr. Munia Ganguli, deals with the preparation methodologies for inorganic nanoparticles using macro- and microemulsions as "microreactor". There are several differences between these two emulsions, in addition to water droplet size: thermodynamic stability, and fusion-redispersion dynamics of the droplets. The properties of the nanoparticles prepared in these emulsion systems are seriously influenced and controlled by the selection of dynamic and static conditions.
Microcluster Physics provides a lucid account of the fundamental physics of all types of microclusters, outlining the dynamics and static properties of this new phase of matter intermediate between a solid and a molecule. Since originally published in 1991, the field of microclusters has experienced surprising developments, which are reviewed in this new edition: The determination of atomic structure, spontaneous alloying, super-shell, fission, fragmentation, evaporation, magnetism, fullerenes, nanotubes, atomic structure of large silicon clusters, superfluidity of a He cluster, water clusters in liquid, electron correlation and optimizsation of the geometry, and scattering.
Maximum Entropy (ME) techniques have found widespread applicability in the reconstruction of incomplete or noisy data. These techniques have been applied in many areas of data analysis including imaging, spectroscopy, and scattering [Gull and Skilling, 1984]. The techniques have proven particularly useful in astronomy [Narayan and Nityanada, 1984]. In many of these applications the goal of the reconstruction is the detection of point objects against a noisy background. In this work we investigate the applicability of ME techniques to data sets which have strong components which are periodic in space or time. The specific interest in our laboratory is High Resolution Electron Micrographs of beam sensitive materials. However, ME techniques are of general interest for all types of data. These data mayor may not have a spatial or temporal character. Figure 1 shows an HREM image of the rigid-rod polymer poly(paraphenylene benzobisoxazole) (PBZO). The 0.55 nm spacings in the image correspond to the lateral close-packing between the extended polymer molecules. Near the center of this crystallite there is evidence for an edge dislocation. In HREM images both the frequency and position of the infonnation is important for a proper interpretation. Therefore, it is necessary to consider how image processing affects the fidelity of this information in both real and Fourier space.
A humoristic view of the physics of soft matter, which nevertheless has a ring of truth to it, is that it is an ill-defined subject which deals with ill-condensed matter by ill-defined methods. Although, since the Nobel prize was awarded to Pierre-Gilles de Gennes, this subject can be no longer shrugged-away as "sludge physics" by the physics community, it is still not viewed universally as "main stream" physics. While, at first glance, this may be considered as another example of inertia, a case of the "establishment" against the "newcomer", the roots of this prejudice are much deeper and can be traced back to Roger Bacon's conception about the objectivity of science. All of us would agree with the weaker form of this idea which simply says that the final results of our work should be phrased in an observer-independent way and be communicable to anybody who made the effort to learn this language. There exists, however, a stronger form of this idea according to which the above criteria of "objectivity" and "communicability" apply also to the process of scientific inquiry. The fact that major progress in the physics of soft matter was made in apparent violation of this approach, by applying intuition to problems which appeared to defy rigorous analysis, may explain why many physicists feel somewhat ill-at-ease with this subject.
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 |
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