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Seven chapters summarize the current status of organometallic cluster chemistry from the viewpoints of synthesis, structure and bonding, ligand substitution reactions, ligand transformations, polyhedral rearrangement, cluster fragmentation reactions, and metal clusters as homogeneous catalysts. An eighth provides an extensive bibliography of reviews for the period from 1965 to 1988. Annotation copyrighted by Book News, Inc., Portland, OR
On Friday, February 20, 1980, I had the pleasure to be present at the inaugural lecture of my colleague Jan Reedijk, who had just been named at the Chair of Inorganic Chemistry of Leiden University. According to tradition, the ceremony took place in the impressive Hall of the old University Academy Building. In the course of his lecture, Jan mentioned a number of recent developments in chemistry which had struck him as particularly important or interesting. Among those was the synthesis of large metal cluster compounds, and, to my luck, he showed a slide ofthe molecular structure of [PtI9(C)b]4-. (To my luck, since at traditional Leiden University it is quite unusual to show slides at such ceremonies.) This constituted my first acquaintance with this exciting new class of materials. I became immediately fascinated by this molecule, partly because of the esthetic beauty of its fivefold symmetry, partly because as a physicist it struck me that it could be visualized as an "embryonically small" metal particle, embedded in a shell of CO ligands.
A pioneer work on catalysis of organic chemical reactions involving multinuclear metal complexes. Catalysis by Di- and Polynuclear Metal Cluster Complexes surveys the latest developments at the frontier of this exciting field, combining theory with new and original examples of catalytic processes produced by polynuclear metal complexes. An invaluable resource for inorganic and organometallic chemists in industry and R&D, it contains chapters from world experts and scholars on: Concepts and models for characterizing homogeneous reactions catalyzed by transition metal cluster complexes Activation of ruthenium clusters for use in catalysis Catalysis by mixed metal clusters containing gold phosphine groupings Catalysis by sulfido bridged dimolybdenum complexes Dimolybdenum and ditungsten complexes Synthesis of organic compounds catalyzed by transition metal clusters Catalysis with dirhodium (II) complexes Catalytic synthesis of polythioether macrocycles Catalysis of Rh, Rh-Co, and Ir-Co multinuclear complexes and its applications to organic syntheses Bimetallic hydroformylation catalysis Catalysis by colloids Catalysis with palladium clusters Heterometallic clusters for heterogeneous catalysis Supported clusters in catalysis.
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.
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.
The contributors to this book discuss inorganic synthesis reactions, dealing with inorganic synthesis and preparative chemistry under specific conditions. They go on to describe the synthesis, preparation and assembly of six important categories of compounds with wide coverage of distinct synthetic chemistry systems
Metal ions play an important role in analytical chemistry, organometallic chemistry, bioinorganic chemistry, and materials chemistry. This book, Descriptive Inorganic Chemistry Researches of Metal Compounds, collects research articles, review articles, and tutorial description about metal compounds. To perspective contemporary researches of inorganic chemistry widely, the kinds of metal elements (typical and transition metals including rare earth; p, d, f-blocks) and compounds (molecular coordination compounds, ionic solid materials, or natural metalloenzyme) or simple substance (bulk, clusters, or alloys) to be focused are not limited. In this way, review chapters of current researches are collected in this book.
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.
"One impressive and compressive book. . . . This review would have to be book size to do full justice to all the insights in this volume." —Journal of Metals Online Fully updated and expanded to reflect recent advances, this Fifth Edition of the classic text provides students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications. With increased focus on organic synthesis applications, nanoparticle science, and green chemistry, the Fifth Edition brings this vital resource up to date. New to the Fifth Edition: Chapters have been updated with relevant examples in the field, modern trends, and new applications; the organic applications chapter has been completely rewritten New end-of-chapter problems, along with their solutions Coverage enhanced with developments in nanoparticle science Increased focus on green chemistry An unparalleled pedagogic resource as well as a valuable working reference for professional chemists, with comprehensive coverage and up-to-date information, students and researchers in organic and organometallic chemistry will turn to The Organometallic Chemistry of the Transition Metals, Fifth Edition for the critical information they need on organometallic compounds, their preparation, and their use in synthesis.
The study of crystal structures has had an ever increasing impact on many fields of science such as physics, chemistry, biology, materials science, medicine, pharmacy, metallurgy, mineralogy and geology. Particularly, with the advent of direct methods of structure determination, the data on crystal structures are accumulating at an unbelievable pace and it becomes more and more difficult to oversee this wealth of data. A crude rationalization of the structures of organic compounds and the atom coordinations can be made with the well-known Kekule model, however, no such generally applicable model exists for the structures of inorganiC and particularly intermetallic compounds. There is a need to rationalize the inorganic crystal structures, to find better ways of describing them, of denoting the geometrical relationships between them, of elucidating the electronic factors and of explaining the bonding between the atoms with the aim of not only having a better understanding of the known structures, but also of predicting structural features of new compounds.