Advanced Inorganic Chemistry: Applications in Everyday Life

Description

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 Advanced Inorganic Chemistry: Applications in Everyday Life Copyright Dedication Biography of Author Foreword Preface Acknowledgments Part 1 - Foundations: Concepts inChemical Bonding andStereochemistry ABSTRACT 1 . Electronic Structure: Quantum Theory Revisited 1. Introduction: Why Do We Need to Know Quantum Theory? 2. Quantum Mechanical Description of the Hydrogen Atom 2.1 Quantum numbers and their significance 2.2 Many electron atom 2.2.1 Effects of electron–electron repulsion 2.3 Valence–valence repulsion and term symbols 2.4 Spin–orbit coupling 2 . Molecular Geometries 1. Introduction: Why Do We Need to Know Molecular Geometries or Shapes of Molecules? 2. Shapes of Molecules—Valence Shell Electron Pair Repulsion (VSEPR) Model 2.1 The VSEPR approach 2.2 Specific examples 2.3 Other considerations 3. Nonrigid Shapes of Molecules (Stereochemistry) 3.1 General concept 3.2 Specific examples 3 . Molecular Symmetry—Part I: Point Group Assignment 1. Introduction: Is It Necessary to Learn Molecular Symmetry? 2. Elements of Symmetry 2.1 Symmetry operations 2.2 Operations and elements 2.2.1 Examples 3. Point Groups 3.1 Introduction 3.2 Rules for assigning point groups 3.3 Examples 4 . Group Theory: Matrix Representation and Character Tables 1. Introduction: Is It Necessary to Learn Group Theory? 2. Other Properties of Symmetry Operations 2.1 Sequential operations 2.2 Representations of a group 2.3 Reducible and irreducible representations 2.4 Character tables 3. Applications to Molecular Structure and Properties 3.1 Application to quantum mechanics 3.2 Bonding in a triangular planar structure (AX3 with D3h point group) 3.3 Molecular orbital correlation diagram for trigonal planar structure (BF3) 4. Examples of Other Structures 4.1 Square planar ML4 4.2 The π orbitals of the cyclopentadienide ion, [C5H5]− 5. Molecular Spectroscopy 5.1 Types of molecular motion 5.2 Normal modes of vibration and symmetry Bibliography Part 2: Advanced Topics-1: Introduction to Ligands and Metal Complexes 5 . Ligands and d-Block Metal Complexes 1. Introduction: Is It Necessary to Know About Ligands and Metal Complexes? 2. Transition Metals 2.1 Electronic structures and oxidation states 2.2 Coordination compounds 2.3 Ligands (Lewis bases) 3. Nomenclature of Coordination Compounds 4. Isomerism in Coordination Compounds 4.1 Coordination number=4 6 . Review of Bonding Theories for d-Block Metal Complexes 1. Introduction: Why Bonding Theories of Metal Complexes Are Important? 2. Valence Bond Theory 2.1 Coordination compounds 2.2 Coordination number six 2.3 Coordination number four 3. Crystal Field Theory 3.1 Octahedral complexes 3.1.1 Experimental evidence for crystal field stabilization 3.2 Complexes of other geometries 3.2.1 Tetrahedral complexes 3.2.2 Square planar complexes 3.2.3 Complexes in a trigonal bipyramidal field 3.3 Trends in crystal field stabilization energy (Δ) 3.4 Predictions using crystal field theory: spin pairing of complexes 3.4.1 Octahedral complexes 3.4.2 Tetrahedral complexes 3.4.3 Square planar complexes 3.5 Distortions due to CFSE 4. Molecular Orbital Theory 4.1 Octahedral complexes 4.2 Other geometries 4.2.1 Tetrahedral complexes 4.2.2 Square planar complexes 4.3 π Bonding in octahedral complexes 4.4 Back π bonding and the effective atomic number rule 4.5 Arene complexes 4.6 Other arene-like ligands 4.7 Benzene sandwich complexes 7 . Coordination Chemistry: Reaction Mechanisms and Their Influencing Factors 1. Introduction: What Makes Coordination Chemistry Interesting? 2. Modes of Substitution Reaction Mechanisms 2.1 Associative mode (a) (or an a intimate mechanism) 2.2 Dissociative mode (d) (or a d intimate mechanism) 3. Complications Involving Metal Complexes 3.1 Solvent competition 3.2 Effects of changing the other ligands on the complex 4. Activation Parameters 4.1 Enthalpy and entropy of activation 4.2 Activation volume, ΔV‡ 4.3 Use of activation parameters in mechanistic studies 5. Examples of Different Coordination Numbers With Geometries and Factors Influencing Reaction Mechanism 5.1 Two- to six-coordinate complexes 5.2 Three-coordinate complexes 5.3 Four-coordinate complexes 5.3.1 Tetrahedral complexes of group 13 5.3.2 Tetrahedral complexes of group 14 (Si, Ge, Sn, and Pb) 5.4 Five-coordinate complexes of phosphorus and sulfur 5.5 Square planar complexes 5.6 Trans effect 5.7 Kinetic effect 5.8 Use of the trans effect in synthesis 5.9 Six-coordinate octahedral complexes 5.10 Isomerization during substitution 5.11 Base hydrolysis 5.12 Other complexes 5.12.1 Heavier group 9 metals 5.13 Electron transfer reactions 5.13.1 Inner sphere mechanism 5.13.2 Outer sphere mechanisms Bibliography Part 3: Advanced Topics-2: Electronic Spectra, Clusters & Isolobal Fragments 8 . Coordination Chemistry: Electronic Spectra 1. Introduction: Why Do We Need to Learn Electronic Spectra? 2. Electronic Spectra 2.1 Selection rules 2.2 Spectra of octahedral (Oh) and tetrahedral (Td) complexes 2.3 Orgel diagrams 2.3.1 Simple one-electron approach 2.3.2 Effect of distortion 2.3.3 Systems arising from F states 3. Tanabe–Sugano Diagrams 4. Charge Transfer Spectra 9 . Cluster Chemistry and Isolobal Fragments 1. Introduction: Role of Cluster Chemistry in Nature 2. Clusters of Boranes, Carboranes, and Their Metal Complexes 2.1 Terminology used in polyhedral boron clusters 2.2 Bonding in boron clusters 2.3 Nomenclature: Wade's rules and structural pattern 3. Clusters of Other Main Group Elements and Transition Metals 3.1 Zintl anions 3.2 Other main group cages 4. Extension of Wade's Rules Beyond Boron Clusters 4.1 Mixed main group/transition metal clusters 4.2 Capping groups 4.3 Condensed clusters 4.4 Clusters with interstitial atoms 4.5 Isolobal relationships 4.6 Isolobal relationships with fragments not derived from noble gas structures Bibliography Part 4: Advanced Topics-3: Organometallic Chemistry and Catalysis 10 . Organometallic Chemistry 1. INTRODUCTION: WHAT IS IN ORGANOMETALLIC CHEMISTRY? 2. DEFINITIONS AND NOMENCLATURE OF ORGANOMETALLIC COMPOUNDS 2.1 Types of organometallic compounds 2.2 IUPAC nomenclature for organometallic compounds 3. MOLECULAR FORMULAS AND STRUCTURES OF ORGANOMETALLIC COMPOUNDS 3.1 Effective atomic number rule 3.2 Metal carbonyls 3.3 Alkene complexes 3.4 Aromatic complexes BIBLIOGRAPHY 11 . Catalysis With Organometallics 1. Introduction: What Is so Special About Catalytic Processes in Our Daily Life? 2. Homogeneous Catalysts 2.1 Oxidative addition and reductive elimination 2.2 Insertion reaction (ligand migration reactions) 3. Hydrogenation Catalysts 3.1 Wilkinson's catalyst, RhCl(PPh3)3 3.2 Monohydride complexes 3.3 Hydroformylation and other closely related oxo processes 4. Other Catalytic Processes 4.1 Production of acetic acid from CH3OH 4.2 Heterogeneous catalysis of alkene polymerization with Ziegler–Natta catalyst 4.3 Suzuki–Miyaura cross-coupling reaction 4.4 Sonogashira cross-coupling reaction 4.5 Olefin metathesis with Grubbs and Schrock catalysts Bibliography Part 5: Advanced Topics-4: Bioinorganic Chemistry and Applications 12 . Bioinorganic Chemistry and Applications 1. Introduction 2. History and Medical Relevance 2.1 Salvarsan 2.2 Vitamin B12 2.3 Cisplatin and cancer treatments 2.4 Other therapeutic applications of organometallic compounds 2.5 Diagnostic metallodrugs 3. Transport and Storage of Metal Ions 3.1 Iron storage: transferrin 3.2 Iron storage: ferritin 3.3 Siderophores 3.4 Sodium–potassium pump 4. Oxygen Transport and Activation Proteins 4.1 Hemoglobin 4.2 Myoglobin 4.3 Hemocyanin 5. Biomineralization Bibliography Index A B C D E F G H I J K L M N O P Q R S T V W Z