Inorganic Chemistry 5th

Description

With its updates to quickly changing content areas, a strengthened visual presentation and the addition of new co-author Paul Fischer, the new edition of this highly readable text is more educational and valuable than ever. Inorganic Chemistry, 5/e delivers the essentials of Inorganic Chemistry at just the right level for today's classroom -- neither too high (for novice readers) nor too low (for advanced readers). Strong coverage of atomic theory and an emphasis on physical chemistry provide a firm understanding of the theoretical basis of inorganic chemistry, while a reorganized presentation of molecular orbital and group theory highlights key principles more clearly. Cover Title Page Copyright Page Brief Contents Contents Preface Dedication and Acknowledgments Chapter 1 Introduction to Inorganic Chemistry 1.1 What Is Inorganic Chemistry? 1.2 Contrasts with Organic Chemistry 1.3 The History of Inorganic Chemistry 1.4 Perspective General References Chapter 2 Atomic Structure 2.1 Historical Development of Atomic Theory 2.1.1 The Periodic Table 2.1.2 Discovery of Subatomic Particles and the Bohr Atom 2.2 The Schrödinger Equation 2.2.1 The Particle in a Box 2.2.2 Quantum Numbers and Atomic Wave Functions 2.2.3 The Aufbau Principle 2.2.4 Shielding 2.3 Periodic Properties of Atoms 2.3.1 Ionization Energy 2.3.2 Electron Affinity 2.3.3 Covalent and Ionic Radii General References Problems Chapter 3 Simple Bonding Theory 3.1 Lewis Electron-Dot Diagrams 3.1.1 Resonance 3.1.2 Higher Electron Counts 3.1.3 Formal Charge 3.1.4 Multiple Bonds in Be and B Compounds 3.2 Valence Shell Electron-Pair Repulsion 3.2.1 Lone-Pair Repulsion 3.2.2 Multiple Bonds 3.2.3 Electronegativity and Atomic Size Effects 3.2.4 Ligand Close Packing 3.3 Molecular Polarity 3.4 Hydrogen Bonding General References Problems Chapter 4 Symmetry and Group Theory 4.1 Symmetry Elements and Operations 4.2 Point Groups 4.2.1 Groups of Low and High Symmetry 4.2.2 Other Groups 4.3 Properties and Representations of Groups 4.3.1 Matrices 4.3.2 Representations of Point Groups 4.3.3 Character Tables 4.4 Examples and Applications of Symmetry 4.4.1 Chirality 4.4.2 Molecular Vibrations General References Problems Chapter 5 Molecular Orbitals 5.1 Formation of Molecular Orbitals from Atomic Orbitals 5.1.1 Molecular Orbitals from s Orbitals 5.1.2 Molecular Orbitals from p Orbitals 5.1.3 Molecular Orbitals from d Orbitals 5.1.4 Nonbonding Orbitals and Other Factors 5.2 Homonuclear Diatomic Molecules 5.2.1 Molecular Orbitals 5.2.2 Orbital Mixing 5.2.3 Diatomic Molecules of the First and Second Periods 5.2.4 Photoelectron Spectroscopy 5.3 Heteronuclear Diatomic Molecules 5.3.1 Polar Bonds 5.3.2 Ionic Compounds and Molecular Orbitals 5.4 Molecular Orbitals for Larger Molecules 5.4.1 FHF- 5.4.2 CO2 5.4.3 H2O 5.4.4 NH3 5.4.5 CO2 Revisited with Projection Operators 5.4.6 BF3 5.4.7 Hybrid Orbitals General References Problems Chapter 6 Acid–Base and Donor–Acceptor Chemistry 6.1 Acid–Base Models as Organizing Concepts 6.1.1 History of Acid–Base Models 6.2 Arrhenius Concept 6.3 Brønsted–Lowry Concept 6.3.1 Nonaqueous Solvents and Acid–Base Strength 6.3.2 Brønsted–Lowry Superacids 6.3.3 Thermodynamic Measurements in Solution 6.3.4 Brønsted–Lowry Gas-Phase Acidity and Basicity 6.3.5 Brønsted–Lowry Superbases 6.3.6 Trends in Brønsted–Lowry Basicity 6.3.7 Brønsted–Lowry Acid Strength of Binary Hydrogen Compounds 6.3.8 Brønsted–Lowry Strength of Oxyacids 6.3.9 Brønsted–Lowry Acidity of Aqueous Cations 6.4 Lewis Acid–Base Concept and Frontier Orbitals 6.4.1 Frontier Orbitals and Acid–Base Reactions 6.4.2 Spectroscopic Support for Frontier Orbital Interactions 6.4.3 Quantification of Lewis Basicity 6.4.4 The BF3 Affinity Scale for Lewis Basicity 6.4.5 Halogen Bonds 6.4.6 Inductive Effects on Lewis Acidity and Basicity 6.4.7 Steric Effects on Lewis Acidity and Basicity 6.4.8 Frustrated Lewis Pairs 6.5 Intemolecular Forces 6.5.1 Hydrogen Bonding 6.5.2 Receptor–Guest Interactions* 6.6 Hard and Soft Acids and Bases 6.6.1 Theory of Hard and Soft Acids and Bases 6.6.2 HSAB Quantitative Measures General References Problems Chapter 7 The Crystalline Solid State 7.1 Formulas and Structures 7.1.1 Simple Structures 7.1.2 Structures of Binary Compounds 7.1.3 More Complex Compounds 7.1.4 Radius Ratio 7.2 Thermodynamics of Ionic Crystal Formation 7.2.1 Lattice Energy and the Madelung Constant 7.2.2 Solubility, Ion Size, and HSAB 7.3 Molecular Orbitals and Band Structure 7.3.1 Diodes, the Photovoltaic Effect, and Light-Emitting Diodes 7.3.2 Quantum Dots 7.4 Superconductivity 7.4.1 Low-Temperature Superconducting Alloys 7.4.2 The Theory of Superconductivity (Cooper Pairs) 7.4.3 High-Temperature Superconductors: YBa2Cu3O7 and Related Compounds 7.5 Bonding in Ionic Crystals 7.6 Imperfections in Solids 7.7 Silicates General References Problems Chapter 8 Chemistry of the Main Group Elements 8.1 General Trends in Main Group Chemistry 8.1.1 Physical Properties 8.1.2 Electronegativity 8.1.3 Ionization Energy 8.1.4 Chemical Properties 8.2 Hydrogen 8.2.1 Chemical Properties 8.3 Group 1: The Alkali Metals 8.3.1 The Elements 8.3.2 Chemical Properties 8.4 Group 2: The Alkaline Earths 8.4.1 The Elements 8.4.2 Chemical Properties 8.5 Group 13 8.5.1 The Elements 8.5.2 Other Chemistry of the Group 13 Elements 8.6 Group 14 8.6.1 The Elements 8.6.2 Compounds 8.7 Group 15 8.7.1 The Elements 8.7.2 Compounds 8.8 Group 16 8.8.1 The Elements 8.9 Group 17: The Halogens 8.9.1 The Elements 8.10 Group 18: The Noble Gases 8.10.1 The Elements 8.10.2 Chemistry of Group 18 Elements General References Problems Chapter 9 Coordination Chemistry I: Structures and Isomers 9.1 History 9.2 Nomenclature 9.3 Isomerism 9.3.1 Stereoisomers 9.3.2 4-Coordinate Complexes 9.3.3 Chirality 9.3.4 6-Coordinate Complexes 9.3.5 Combinations of Chelate Rings 9.3.6 Ligand Ring Conformation 9.3.7 Constitutional Isomers 9.3.8 Separation and Identification of Isomers 9.4 Coordination Numbers and Structures 9.4.1 Coordination Numbers 1, 2, and 3 9.4.2 Coordination Number 4 9.4.3 Coordination Number 5 9.4.4 Coordination Number 6 9.4.5 Coordination Number 7 9.4.6 Coordination Number 8 9.4.7 Larger Coordination Numbers 9.5 Coordination Frameworks General References Problems Chapter 10 Coordination Chemistry II: Bonding 10.1 Evidence for Electronic Structures 10.1.1 Ther modynamic Data 10.1.2 Magnetic Susceptibility 10.1.3 Electronic Spectra 10.1.4 Coordination Numbers and Molecular Shapes 10.2 Bonding Theories 10.2.1 Crystal Field Theory 10.3 Ligand Field Theory 10.3.1 Molecular Orbitals for Octahedral Complexes 10.3.2 Orbital Splitting and Electron Spin 10.3.3 Ligand Field Stabilization Energy 10.3.4 Square-Planar Complexes 10.3.5 Tetrahedral Complexes 10.4 Angular Overlap 10.4.1 Sigma-Donor Interactions 10.4.2 Pi-Acceptor Interactions 10.4.3 Pi-Donor Interactions 10.4.4 The Spectrochemical Series 10.4.5 Magnitudes of e base σ, e base π, and Δ 10.4.6 A Magnetochemical Series 10.5 The Jahn–Teller Effect 10.6 Four- and Six-Coordinate Preferences 10.7 Other Shapes General References Problems Chapter 11 Coordination Chemistry III: Electronic Spectra 11.1 Absorption of Light 11.1.1 Beer–Lambert Absorption Law 11.2 Quantum Numbers of Multielectron Atoms 11.2.1 Spin-Orbit Coupling 11.3 Electronic Spectra of Coordination Compounds 11.3.1 Selection Rules 11.3.2 Correlation Diagrams 11.3.3 Tanabe–Sugano Diagrams 11.3.4 Jahn–Teller Distortions and Spectra 11.3.5 Applications of Tanabe–Sugano Diagrams: Determining Δ base o from Spectra 11.3.6 Tetrahedral Complexes 11.3.7 Charge-Transfer Spectra 11.3.8 Charge-Transfer and Energy Applications General References Problems Chapter 12 Coordination Chemistry IV: Reactions and Mechanisms 12.1 Background 12.2 Substitution Reactions 12.2.1 Inert and Labile Compounds 12.2.2 Mechanisms of Substitution 12.3 Kinetic Consequences of Reaction Pathways 12.3.1 Dissociation (D) 12.3.2 Interchange (I) 12.3.3 Association (A) 12.3.4 Preassociation Complexes 12.4 Experimental Evidence in Octahedral Substitution 12.4.1 Dissociation 12.4.2 Linear Free-Energy Relationships 12.4.3 Associative Mechanisms 12.4.4 The Conjugate Base Mechanism 12.4.5 The Kinetic Chelate Effect 12.5 Stereochemistry of Reactions 12.5.1 Substitution in trans Complexes 12.5.2 Substitution in cis Complexes 12.5.3 Isomerization of Chelate Rings 12.6 Substitution Reactions of Square-Planar Complexes 12.6.1 Kinetics and Stereochemistry of Square-Planar Substitutions 12.6.2 Evidence for Associative Reactions 12.7 The trans Effect 12.7.1 Explanations of the trans Effect27 12.8 Oxidation–Reduction Reactions 12.8.1 Inner-Sphere and Outer-Sphere Reactions 12.8.2 Conditions for High and Low Oxidation Numbers 12.9 Reactions of Coordinated Ligands 12.9.1 Hydrolysis of Esters, Amides, and Peptides 12.9.2 Template Reactions 12.9.3 Electrophilic Substitution General References Problems Chapter 13 Organometallic Chemistry 13.1 Historical Background 13.2 Organic Ligands and Nomenclature 13.3 The 18-Electron Rule 13.3.1 Counting Electrons 13.3.2 Why 18 Electrons? 13.3.3 Square-Planar Complexes 13.4 Ligands in Organometallic Chemistry 13.4.1 Carbonyl (CO) Complexes 13.4.2 Ligands Similar to CO 13.4.3 Hydride and Dihydrogen Complexes 13.4.4 Ligands Having Extended Pi Systems 13.5 Bonding between Metal Atoms and Organic Pi Systems 13.5.1 Linear Pi Systems 13.5.2 Cyclic Pi Systems 13.5.3 Fullerene Complexes 13.6 Complexes Containing M-C, M=C, and M triple bond C Bonds 13.6.1 Alkyl and Related Complexes 13.6.2 Carbene Complexes 13.6.3 Carbyne (Alkylidyne) Complexes 13.6.4 Carbide and Cumulene Complexes 13.6.5 Carbon Wires: Polyyne and Polyene Bridges 13.7 Covalent Bond Classification Method 13.8 Spectral Analysis and Characterization of Organometallic Complexes 13.8.1 Infrared Spectra 13.8.2 NMR Spectra 13.8.3 Examples of Characterization General References Problems Chapter 14 Organometallic Reactions and Catalysis 14.1 Reactions Involving Gain or Loss of Ligands 14.1.1 Ligand Dissociation and Substitution 14.1.2 Oxidative Addition and C—H Bond Activation 14.1.3 Reductive Elimination and Pd-Catalyzed Cross-Coupling 14.1.4 Sigma Bond Metathesis 14.1.5 Application of Pincer Ligands 14.2 Reactions Involving Modification of Ligands 14.2.1 Insertion 14.2.2 Carbonyl Insertion (Alkyl Migration) 14.2.3 Examples of 1,2 Insertions 14.2.4 Hydride Elimination 14.2.5 Abstraction 14.3 Organometallic Catalysts 14.3.1 Catalytic Deuteration 14.3.2 Hydroformylation 14.3.3 Monsanto Acetic Acid Process 14.3.4 Wacker (Smidt) Process 14.3.5 Hydrogenation by Wilkinson’s Catalyst 14.3.6 Olefin Metathesis 14.4 Heterogeneous Catalysts 14.4.1 Ziegler–Natta Polymerizations 14.4.2 Water Gas Reaction General References Problems Chapter 15 Parallels between Main Group and Organometallic Chemistry 15.1 Main Group Parallels with Binary Carbonyl Complexes 15.2 The Isolobal Analogy 15.2.1 Extensions of the Analogy 15.2.2 Examples of Applications of the Analogy 15.3 Metal–Metal Bonds 15.3.1 Multiple Metal–Metal Bonds 15.4 Cluster Compounds 15.4.1 Boranes 15.4.2 Heteroboranes 15.4.3 Metallaboranes and Metallacarboranes 15.4.4 Carbonyl Clusters 15.4.5 Carbon-Centered Clusters 15.4.6 Additional Comments on Clusters General References Problems Appendix A: Answers to Exercises Appendix C: Character Tables Index Pearson Advanced Chemistry Series Periodic Table of Elements Greek Alphabet/Names and Symbols for the Elements Electron Configurations of the Elements Physical Constants/Conversion Factors