This book discusses current techniques and instrumentation for cluster chemistry. It addresses both the experimental and theoretical aspects of gas-phase metal cluster reactivities, especially those pertaining to pollution removal, energetic reactions and corrosion and anticorrosion. These metal cluster systems have attracted enormous interest as they display a completely new class of physical, chemical, electronic, magnetic and catalytic properties. As these properties change with size and composition, it can thus be understood how their nature evolves from atoms to bulk solids. The book offers readers a basic understanding of the structural chemistry and reactivity of metal clusters in both gas-phase and wet chemistry. Further, the lessons they learn here regarding metal cluster chemistry will prepare researchers for the study of condensed phase dynamics that pertain to wet chemical synthesis, soft-landing deposition and cluster assembly.
Transition metal carbonyl clusters (TMCCs) continue to inspire great interest in chemical research, as much for their fascinating structures as for potential industrial applications conferred by their unique properties. This highly accessible book introduces the bonding, structure, spectroscopic properties, and characterization of clusters, and then explores their synthesis, reactivity, reaction mechanisms and use in organic synthesis and catalysis. Transition Metal Carbonyl Cluster Chemistry describes models and rules that correlate cluster structure with electron count, which are then applied in worked examples. Subsequent chapters explain how bonding relates to molecular structure, demonstrate the use of spectroscopic techniques such as NMR, IR and MS in cluster chemistry, and outline the factors contributing to the stability, dynamics and reactivity of clusters. The second part of this book discusses the synthesis and applications of TMCCs. It emphasizes the differences between the reactivities of clusters vs. mononuclear metal complexes, contingent to the availability of multiple-bonding sites and heterosite reactivity. The final chapters discuss reactions in which clusters act as homogeneous catalysts; including discussion on the use of solid and biphasic liquid-liquid supported clusters in heterogeneous catalysts. A useful reference for those commencing further research or post-graduate study on metal carbonyl clusters and advanced organometallic chemistry, this book is also a cornerstone addition to academic and libraries as well as private collections.
Atomic clusters are aggregates of atoms containing a few to several thousand atoms. Due to the small size of these pieces of matter, the properties of atomic clusters in general are different from those of the corresponding material in the macroscopic bulk phase. This monograph presents the main developments of atomic clusters and the current status of the field. The book treats different types of clusters with very different properties: clusters in which the atoms or molecules are tied by weak van der Waals interactions, metallic clusters, clusters of ionic materials, and network clusters made of typical covalent elements. It includes methods of experimental cluster synthesis as well as the structural, electronic, thermodynamic and magnetic properties of clusters, covering both experiments and the theoretical work that has led to our present understanding of the different properties of clusters. The question of assembling nanoclusters to form solids with new properties is also considered. Having an adequate knowledge of the properties of clusters can be of great help to any scientist working with objects of nanometric size. On the other hand, nanoclusters are themselves potentially important in fields like catalysis and nanomedicine.
Cluster chemistry is one of the recent, exciting areas of Inorganic Chemistry. The occurence of molecular clusters, like fullerene C60, constitutes a fundamental feature midway between the chemistry of isolated chemical compounds and that of the elements. Main features of the Cluster Chemistry of both main group and transition metal elements are treated in this book. The author highlights aspects releated to the synthesis, the structure, the special bonding and the reactivity of these species. The book is written as a textbook for senior undergraduate and postgraduate students. References in tables andillustrations permit the reader to reach relevant original information. Professor Gonzalez-Moraga fills a demand for a publication appropriate for dissemination and specially for teaching this exciting subject. From the Contents: Current Concepts in Modern Chemistry - Transition Metal Cluster Chemistry - Main Group-Transition Metal Mixed Clusters - Cluster Compounds of the Main Group Elements - Synthetic Analogues of the Active Sites of Iron-Sulfur Proteins.
An advanced-level textbook of inorganic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of four volume series, entitled "A Textbook of Inorganic Chemistry – Volume I, II, III, IV". CONTENTS: Chapter 1. Stereochemistry and Bonding in Main Group Compounds: VSEPR theory; dπ -pπ bonds; Bent rule and energetic of hybridization. Chapter 2. Metal-Ligand Equilibria in Solution: Stepwise and overall formation constants and their interactions; Trends in stepwise constants; Factors affecting stability of metal complexes with reference to the nature of metal ion and ligand; Chelate effect and its thermodynamic origin; Determination of binary formation constants by pH-metry and spectrophotometry. Chapter 3. Reaction Mechanism of Transition Metal Complexes – I: Inert and labile complexes; Mechanisms for ligand replacement reactions; Formation of complexes from aquo ions; Ligand displacement reactions in octahedral complexes- acid hydrolysis, base hydrolysis; Racemization of tris chelate complexes; Electrophilic attack on ligands. Chapter 4. Reaction Mechanism of Transition Metal Complexes – II: Mechanism of ligand displacement reactions in square planar complexes; The trans effect; Theories of trans effect; Mechanism of electron transfer reactions – types; outer sphere electron transfer mechanism and inner sphere electron transfer mechanism; Electron exchange. Chapter 5. Isopoly and Heteropoly Acids and Salts: Isopoly and Heteropoly acids and salts of Mo and W: structures of isopoly and heteropoly anions. Chapter 6. Crystal Structures: Structures of some binary and ternary compounds such as fluorite, antifluorite, rutile, antirutile, crystobalite, layer lattices- CdI2, BiI3; ReO3, Mn2O3, corundum, pervoskite, Ilmenite and Calcite. Chapter 7. Metal-Ligand Bonding: Limitation of crystal field theory; Molecular orbital theory: octahedral, tetrahedral or square planar complexes; π-bonding and molecular orbital theory. Chapter 8. Electronic Spectra of Transition Metal Complexes: Spectroscopic ground states, Correlation and spin-orbit coupling in free ions for Ist series of transition metals; Orgel and Tanabe-Sugano diagrams for transition metal complexes (d1 – d9 states); Calculation of Dq, B and β parameters; Effect of distortion on the d-orbital energy levels; Structural evidence from electronic spectrum; John-Tellar effect; Spectrochemical and nephalauxetic series; Charge transfer spectra; Electronic spectra of molecular addition compounds. Chapter 9. Magantic Properties of Transition Metal Complexes: Elementary theory of magneto - chemistry; Guoy’s method for determination of magnetic susceptibility; Calculation of magnetic moments; Magnetic properties of free ions; Orbital contribution, effect of ligand-field; Application of magneto-chemistry in structure determination; Magnetic exchange coupling and spin state cross over. Chapter 10. Metal Clusters: Structure and bonding in higher boranes; Wade’s rules; Carboranes; Metal carbonyl clusters - low nuclearity carbonyl clusters; Total electron count (TEC). Chapter 11. Metal-π Complexes: Metal carbonyls: structure and bonding; Vibrational spectra of metal carbonyls for bonding and structure elucidation; Important reactions of metal carbonyls; Preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; Tertiary phosphine as ligand.
Heterogeneous catalysis provides the backbone of the world's chemical and oil industries. The innate complexity of practical catalytic systems suggests that useful progress should be achievable by investigating key aspects of catalysis by experimental studies on idealised model systems. Thin films and supported clusters are two promising types of model system that can be used for this purpose, since they mimic important aspects of the properties of practical dispersed catalysts. Similarly, appropriate theoretical studies of chemisorption and surface reaction clusters or extended slab systems can provide valuable information on the factors that underlie bonding and catalytic activity. This volume describes such experimental and theoretical approaches to the surface chemistry and catalytic behaviour of metals, metal oxides and metal/metal oxide systems. An introduction to the principles and main themes of heterogeneous catalysis is followed by detailed accounts of the application of modern experimental and theoretical techniques to fundamental problems. The application of advanced experimental methods is complemented by a full description of theoretical procedures, including Hartree-Fock, density functional and similar techniques. The relative merits of the various approaches are considered and directions for future progress are indicated.
Clusters can be viewed as solids at the nano-scale, yet molecular cluster chemistry and solid state chemistry have traditionally been considered as separate topics. This treatment has made it conceptually difficult to appreciate commonalities of structure and bonding between the two. Using analogous models, this is the first book to form a connecting bridge. Although the focus is on clusters, sufficient attention is paid to solid-state compounds at each stage of the development to establish the interrelationship between the two topics. Comprehensive coverage of cluster types by composition, size and ligation, is provided, as is a synopsis of selected research. Written in an accessible style and highly illustrated to aid understanding, this book is suitable for researchers in inorganic chemistry, physical chemistry, materials science, and condensed matter physics.
Metal Nanoclusters in Catalysis and Materials Science: The Issue of Size Control deals with the synthesis of metal nanoclusters along all known methodologies. Physical and chemical properties of metal nanoclusters relevant to their applications in chemical processing and materials science are covered thoroughly. Special attention is given to the role of metal nanoclusters size and shape in catalytic processes and catalytic applications relevant to industrial chemical processing.An excellent text for expanding the knowledge on the chemistry and physics of metal nanoclusters. Divided in two parts; Part I deals with general aspects of the matter and Part II has to be considered a useful handbook dealing with the production of metal nanoclusters, especially from their size-control point of view.* Divided into two parts for ease of reference: general and operational * Separation of synthetic aspects, physical properties and applications* Specific attention is given to the task of metal nanoclusters size-control
Reactions with metals are ubiquitous in organic synthesis and, particularly in the last few years, a large repertoire of methods for the activation of metals and for their use in organic synthesis has been developed. In Active Metals, topics ranging from morphology of metal clusters and nanometallurgy to organometallic chemistry, catalysis and the use of activated metals in natural product synthesis are authoritatively discussed by leading experts in the field. Active Metals will allow you to fully benefit from the recent advances in the field by giving: * Detailed experimental procedures * Guidance on manipulation of active metals under inert atmosphere * Valuable information for planning syntheses * Extensive tables of typical conversions with yields * Critically selected, up-to-date references This handbook is a unique source of 'hands-on' information which will allow you to expand the scope of your research.
