A Textbook of Inorganic Chemistry – Volume 1


Book Description

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.




Spectroscopic Studies of Ground and Excited State Mixed Valence


Book Description

Mixed valence systems have two charge bearing units (M) that share a radical electron. Coupling between the sites is mediated by a covalent bridge (B). These systems have been extensively studied since the 1960's on account of their interesting electronic structure and as an ideal system for understanding intermolecular electron transfer. One of the characteristic signatures of mixed valence is the intervalence charge transfer (IVCT): a low energy electronic absorption where the radical electron is formally transferred from one site to the other. However, this phenomenon is not unique to the ground state and has also been shown to occur in the excited state. In the electronic absorption spectrum excited state mixed valence manifests as a set of two transitions. The first three studies presented in this dissertation will focus on understanding the excited state geometric distortions upon photoexcitation of ground state and excited state mixed valence systems. The first chapter of this dissertation is an introduction to the underlying principles and history of excited state mixed valence. Important tools to analyze and interpret mixed valence systems which are used throughout the remainder of this dissertation are presented including the neighboring orbital model and the time-dependent theory of spectroscopy. Several aspects of these tools as they apply to the coupling and transition dipole moments are presented through three historical models and additional pedagogical examples. The following three chapters are fundamental studies of mixed valence systems. The first study investigates the relationship between ground and excited state mixed valence in the radical anion of 9,9-dimethyl-2,7-dinitrofluorene. Apparent similarities in the absorption spectrum are analyzed using time-dependent theory, the neighboring orbital model, and resonance Raman spectroscopy. The second study reviews the excited state mixed valence of diisopropyl ditolyl radical cation. This study presents an essential expansion of the transition dipole moment analysis that is typically applied to excited state mixed valence systems. The third mixed valence study examines the importance of coordinate dependent coupling in a dialkylaniline ether. The ground state geometry of this compound should forbid any coupling between the aniline moieties, however, movement along a low frequency twisting coordinate facilitates coupling giving rise to mixed valence transitions. The final two chapters of this thesis are applied spectroscopic studies. The first applied study characterizes the weak electronic interaction between iron and ruthenium in a ferrocene complex. This is achieved by combining electronic absorption spectroscopy with Raman spectroscopy in resonance with a near IR iron-ruthenium charge transfer. The profile of the iron-ruthenium Raman stretch aids in the assignment of the electronic transition. The second applied study the photoisomerization of an azobenzene based linker in metal organic framework. Photophysical studies are present to understand the dynamics of the linker and subsequently demonstrate the ability of the metal organic framework to store molecular cargo and release it on demand.




Transition Metals in Coordination Environments


Book Description

This book focuses on the electronic properties of transition metals in coordination environments. These properties are responsible for the unique and intricate activity of transition metal sites in bio- and inorganic catalysis, but also pose challenges for both theoretical and experimental studies. Written by an international group of recognized experts, the book reviews recent advances in computational modeling and discusses their interplay using experiments. It covers a broad range of topics, including advanced computational methods for transition metal systems; spectroscopic, electrochemical and catalytic properties of transition metals in coordination environments; metalloenzymes and biomimetic compounds; and spin-related phenomena. As such, the book offers an invaluable resource for all researchers and postgraduate students interested in both fundamental and application-oriented research in the field of transition metal systems.







The Organometallic Chemistry of the Transition Metals


Book Description

Fully updated and expanded to reflect recent advances, this Fourth Edition of the classic text provides students and professional chemists with an excellent 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.




Directory of Graduate Research


Book Description







Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part A


Book Description

The Sixth Edition of this classic work comprises the most comprehensive and current guide to infrared and Raman spectra of inorganic, organometallic, bioinorganic, and coordination compounds. From fundamental theories of vibrational spectroscopy to applications in a variety of compound types, this has been extensively updated. New topics include the theoretical calculations of vibrational frequencies (DFT method), chemical synthesis by matrix co-condensation reactions, time-resolved Raman spectroscopy, and more. This volume is a core reference for chemists and medical professionals working with infrared or Raman spectroscopies and an excellent textbook for graduate courses.