This book starts with the most elementary ideas of molecular orbital theory and leads the reader progressively to an understanding of the electronic structure, geometry and, in some cases, reactivity of transition metal complexes. The qualitative orbital approach, based on simple notions such as symmetry, overlap and electronegativity, is the focus of the presentation and a substantial part of the book is associated with the mechanics of the assembly of molecular orbital diagrams. The first chapter recalls the basis for electron counting in transition metal complexes. The main ligand fields (octahedral, square planar, tetrahedral, etc.) are studied in the second chapter and the structure of the "d block" is used to trace the relationships between the electronic structure and the geometry of the complexes. The third chapter studies the change in analysis when the ligands have pi-type interactions with the metal. All these ideas are then used in the fourth chapter to study a series of selected applications of varying complexity (e.g. structure and reactivity). The fifth chapter deals with the "isolobal analogy" which points out the resemblance between the molecular orbitals of inorganic and organic species and provides a bridge between these two subfields of chemistry. The last chapter is devoted to a presentation of basic Group Theory with applications to some of the complexes studied in the earlier chapters.
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.
This book starts with the most elementary ideas of molecular orbital theory and leads the reader progressively to an understanding of the electronic structure, geometry and, in some cases, reactivity of transition metal complexes. The qualitative orbital approach, based on simple notions such as symmetry, overlap and electronegativity, is the focus of the presentation and a substantial part of the book is associated with the mechanics of the assembly of molecular orbital diagrams. The first chapter recalls the basis for electron counting in transition metal complexes. The main ligand fields (octahedral, square planar, tetrahedral, etc.) are studied in the second chapter and the structure of the "d block" is used to trace the relationships between the electronic structure and the geometry of the complexes. The third chapter studies the change in analysis when the ligands have pi-type interactions with the metal. All these ideas are then used in the fourth chapter to study a series of selected applications of varying complexity (e.g. structure and reactivity). The fifth chapter deals with the "isolobal analogy" which points out the resemblance between the molecular orbitals of inorganic and organic species and provides a bridge between these two subfields of chemistry. The last chapter is devoted to a presentation of basic Group Theory with applications to some of the complexes studied in the earlier chapters.
GEORGE CHRISTOU Indiana University, Bloomington I am no doubt representative of a large number of current inorganic chemists in having obtained my undergraduate and postgraduate degrees in the 1970s. It was during this period that I began my continuing love affair with this subject, and the fact that it happened while I was a student in an organic laboratory is beside the point. I was always enchanted by the more physical aspects of inorganic chemistry; while being captivated from an early stage by the synthetic side, and the measure of creation with a small c that it entails, I nevertheless found the application of various theoretical, spectroscopic and physicochemical techniques to inorganic compounds to be fascinating, stimulating, educational and downright exciting. The various bonding theories, for example, and their use to explain or interpret spectroscopic observations were more or less universally accepted as belonging within the realm of inorganic chemistry, and textbooks of the day had whole sections on bonding theories, magnetism, kinetics, electron-transfer mechanisms and so on. However, things changed, and subsequent inorganic chemistry teaching texts tended to emphasize the more synthetic and descriptive side of the field. There are a number of reasons for this, and they no doubt include the rise of diamagnetic organometallic chemistry as the dominant subdiscipline within inorganic chemistry and its relative narrowness vis-d-vis physical methods required for its prosecution.
With more than 40% new and revised materials, this second edition offers researchers and students in the field a comprehensive understanding of fundamental molecular properties amidst cutting-edge applications. Including ~70 Example-Boxes and summary notes, questions, exercises, problem sets, and illustrations in each chapter, this publication is also suitable for use as a textbook for advanced undergraduate and graduate students. Novel material is introduced in description of multi-orbital chemical bonding, spectroscopic and magnetic properties, methods of electronic structure calculation, and quantum-classical modeling for organometallic and metallobiochemical systems. This is an excellent reference for chemists, researchers and teachers, and advanced undergraduate and graduate students in inorganic, coordination, and organometallic chemistry.
This volume covers both basic and advanced aspects of organometallic chemistry of all metals and catalysis. In order to present a comprehensive view of the subject, it provides broad coverage of organometallic chemistry itself. The catalysis section includes the challenging activation and fictionalization of the main classes of hydrocarbons and the industrially crucial heterogeneous catalysis. Summaries and exercises are provides at the end of each chapter, and the answers to these exercises can be found at the back of the book. Beginners in inorganic, organic and organometallic chemistry, as well as advanced scholars and chemists from academia and industry will find much value in this title.
"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.
Explains the underlying structure that unites all disciplinesin chemistry Now in its second edition, this book explores organic,organometallic, inorganic, solid state, and materials chemistry,demonstrating how common molecular orbital situations arisethroughout the whole chemical spectrum. The authors explore therelationships that enable readers to grasp the theory thatunderlies and connects traditional fields of study withinchemistry, thereby providing a conceptual framework with which tothink about chemical structure and reactivity problems. Orbital Interactions in Chemistry begins by developingmodels and reviewing molecular orbital theory. Next, the bookexplores orbitals in the organic-main group as well as in solids.Lastly, the book examines orbital interaction patterns that occurin inorganic-organometallic fields as well as clusterchemistry, surface chemistry, and magnetism in solids. This Second Edition has been thoroughly revised andupdated with new discoveries and computational tools since thepublication of the first edition more than twenty-five years ago.Among the new content, readers will find: * Two new chapters dedicated to surface science and magneticproperties * Additional examples of quantum calculations, focusing oninorganic and organometallic chemistry * Expanded treatment of group theory * New results from photoelectron spectroscopy Each section ends with a set of problems, enabling readers totest their grasp of new concepts as they progress through the text.Solutions are available on the book's ftp site. Orbital Interactions in Chemistry is written for bothresearchers and students in organic, inorganic, solid state,materials, and computational chemistry. All readers will discoverthe underlying structure that unites all disciplines inchemistry.
Advanced Inorganic Chemistry: Applications in Everyday Life connects key topics on the subject with actual experiences in nature and everyday life. Differing from other foundational texts with this emphasis on applications and examples, the text uniquely begins with a focus on the shapes (geometry) dictating intermolecular forces of attractions, leading to reactivity between molecules of different shapes. From this foundation, the text explores more advanced topics, such as: Ligands and Ligand Substitution Processes with an emphasis on Square-Planar Substitution and Octahedral Substitution Reactions in Inorganic Chemistry and Transition Metal Complexes, with a particular focus on Crystal-Field and Ligand-Field Theories, Electronic States and Spectra and Organometallic, Bioinorganic Compounds, including Carboranes and Metallacarboranes and their applications in Catalysis, Medicine and Pollution Control. Throughout the book, illustrative examples bring inorganic chemistry to life. For instance, biochemists and students will be interested in how coordination chemistry between the transition metals and the ligands has a direct correlation with cyanide or carbon monoxide poisoning (strong-field Cyanide or CO ligand versus weak-field Oxygen molecule). - Engaging discussion of key concepts with examples from the real world - Valuable coverage from the foundations of chemical bonds and stereochemistry to advanced topics, such as organometallic, bioinorganic, carboranes and environmental chemistry - Uniquely begins with a focus on the shapes (geometry) dictating intermolecular forces of attractions, leading to reactivity between molecules of different shapes
The material addressed in this book forms the foundation of undergraduate lecture courses on d-block chemistry and facilitates learning through various key features.
