Ralph G. Wilkins Kinetics and Mechanism of Reactions of Transition Metal Complexes This thoroughly revised and updated edition of one of the classics of kinetics textbooks continues the successful concept of the 1974 edition. It starts with a simplified approach to the determination of rate laws and mechanisms, steadily working up to complex situations. In the following chapters the principles developed there are extensively used in a comprehensive account of reactions of transition metal complexes, including reactions of biological significance. The text is illustrated by numerous figures and tables. Points of further interest are highlighted in special insets. 140 problems, taken from the original literature, enable the student to apply and deepen the newly acquired knowledge and make the book highly useful for courses in inorganic and organometallic reaction mechanisms. Furthermore, a wealth of over 1700 references make the book indispensable for the active researcher.

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.

This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. - Provides a general background as a course module in the area of inorganic reaction mechanisms, which has important research applications in the metallurgical industry - Contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands

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.

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.

Jetzt in neuer Auflage: Das erfolgreiche Lehrwerk über Kinetik und Mechanismen anorganischer und organometallischer Reaktionen für fortgeschrittene Studenten! Hervorragend geeignet als Begleiter eines Vorlesungssemesters. Mit zahlreichen Übungsaufgaben; für eine bessere Übersicht sorgen Zusammenfassungen am Ende jedes Kapitels.