Inorganic Chemistry GARY L. MIESSLER DONALD A. TARR. St. Olaf College Northfield, Minnesota

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1 Inorganic Chemistry GARY L. MIESSLER DONALD A. TARR St. Olaf College Northfield, Minnesota

2 Contents PREFACE xiii 1 INTRODUCTION TO INORGANIC CHEMISTRY What Is Inorganic Chemistry? Contrasts with Organic Chemistry 1 I -3 Genesis of the Elements (The Big Bang) Formation of the Earth Nuclear Reactions and Radioactivity The History of Inorganic Chemistry 11 2 ATOMIC STRUCTURE Historical Development of Atomic Theory The Periodic Table Discovery of Subatomic Particles and the Bohr Atom The Schrödinger Equation The Particle in a Box Atomic Wave Functions Quantum Numbers and Orbitals The Aufbau Principle Shielding Quantum Numbers of Multielectron Atoms Spin-Orbit Coupling Periodic Properties of Atoms Ionization Energy Electron Affinity Covalent and lonic Radii lonic Bonding and Crystal Structures 52 3 SIMPLE BONDING THEORY Lewis Electron-Dot Diagrams Expanded Shells Resonance 61 v

3 3-1-3 Electronegativity and Bond Polarity Formal Charge Formal Charge and Expanded Octets Multiple Bonds in Be and B Compounds Valence Shell Electron Pair Repulsion Theory Lone Pair Repulsion Multiple Bonds Electronegativity Polar Bonds Hydrogen Bonding 77 4 SYMMETRY AIS/D GROUP THEORY Symmetry Elements and Operations Point Groups Properties and Representation of Groups Matrices Representations of Point Groups Character Tables Examples and Applications of Symmetry Chirality Molecular Vibrations MOLECULAR ORBITALS Formation of Molecular Orbitals Bonding in H Molecular Orbitals from p and d Orbitals Homonuclear Diatomic Molecules Colors of Halogen Molecules, X Photoelectron Spectroscopy Correlation Diagrams Heteronuclear Diatomic Molecules Polar Bonds lonic Compounds and Molecular Orbitals A Pictorial Approach to Molecular Orbitals Group Theory Approach to Molecular Orbitals Hybrid Orbitals More Complex Molecules Metals, Semiconductors, and Insulators ACID-BASE AND DONOR-ACCEPTOR CHEMISTRY Acid-Base Concepts as Organizing Concepts History Arrhenius Concept Br<j>nsted Concept Solvent System Concept Lewis Concept Acid and Base Strength Measurement of Acid-Base Interactions Thermodynamic Measurements Proton Affinity Acidity and Basicity of Binary Hydrogen Compounds 185 VI

4 6-3-5 Inductive Effects Strength of Oxyacids Acidity of Cations in Aqueous Solution Steric Effects Nonaqueous Solvents and Acid-Base Strength Superacids Drago's E, C Equation Hard and Soft Acids and Bases Comparison ofhs AB and E, C Solvent Contribution Frontier Orbitals and Acid-Base Reactions Carbon Monoxide Hydrogen Bonding Electronic Spectra (including Charge Transfer) Molecular Orbitals and HSAB CHEA/IISTRY OF THE MAIN GROUP ELEMENTS General Trends in Main Group Chemistry Physical Properties Electronegativity Ionization Energy Chemical Properties Hydrogen Chemical Properties Group 1 (IA): The Alkali Metals The Elements Chemical Properties Group 2 (IIA): The Alkaline Earths The Elements Chemical Properties Group 13 (IIIA) The Elements Other Chemistry of the Group 13 (IIIA) Elements Group 14 (IVA) The Elements Compounds Group 15 (VA) The Elements Group 16 (VIA) The Elements Group 17 (VIIA): The Halogens The Elements Group 18 (VIIIA): The Noble Gases The Elements Chemistry COORDINATION CHEMISTRY I: BONDING History Experimental Evidence for Electronic Structures Thermodynamic Data Magnetic Susceptibility 277 VÜ

5 8-2-3 Electronic Spectra Coordination Numbers and Molecular Shapes Theories of Electronic Structure Ligand Field Theory Orbital Splitting and Electron Spin Ligand Field Stabilization Energy Pi Bonding Angular Overlap Sigma Donor Interactions Pi Acceptor Interactions Pi Donor Interactions Magnitudes of e a, e^, and A Types of Ligands and the Spectrochemical Series The Jahn-Teller Effect Valence Bond Theory Crystal Field Theory Group Theory and Nonoctahedral Complexes COORDINATION CHEMISTRY II: ELECTRONIC SPECTRA Absorption of Light Beer-Lambert Absorption Law Electronic Spectra of Coordination Compounds Selection Rules Correlation Diagrams Tanabe-Sugano Diagrams Jahn-Teller Distortions and Spectra Applications of Tanabe-Sugano Diagrams: Determining \ 0 from Spectra Tetrahedral Complexes Charge Transfer Spectra COORDINATION CHEMISTRY III: STRUCTURES AND ISOMERS Nomenclature Common Structures Low Coordination Numbers (CN =1,2, and 3) Coordination Number Coordination Number Coordination Number Coordination Number Coordination Number Larger Coordination Numbers Four-and Six-Coordinate Preferences Isomerism Stereoisomerism Four-Coordinate Compounds Chirality Six-Coordinate Compounds Combinations of Chelate Rings Ligand Ring Conformation Experimental Separation and Identification of Isomers 365 VÜi

6 Hydrate Isomerism Coordination Isomerism Linkage (Ambidentate) Isomerism Distortional Isomerism COORDINATION CHEMISTRY IV: REACTIONS AND MECHANISMS History Substitution Reactions Inert and Labile Compounds Mechanisms of Substitution Kinetic Consequences of Reaction Pathways Dissociation (D) Interchange (I) Association (A) Experimental Evidence in Octahedral Substitution Dissociation Linear Free Energy Relationships (LFER) Associative Mechanisms The Conjugate Base Mechanism The Chelate Effect Stereochemistry of Reactions Substitution in Cis Complexes Substitution in Trans Complexes Optically Active Compounds Isomerization Pseudorotation Substitution Reactions of Square Planar Complexes Kinetics of Square Planar Substitutions Evidence for Associative Reactions Stereochemistry The Trans Effect Explanations of the Trans Effect Oxidation-Reduction Reactions Inner- and Outer-Sphere Reactions Conditions for High and Low Oxidaüon Numbers Reactions of Coordinated Ligands Hydrolysis of Esters, Amides, and Peptides Template Reactions Electrophilic Substitution ORGANOMETALLIC CHEMISTRY Historical Background Organic Ligands and Nomenclature The 18-Electron Rule Counting Electrons Why 18 Electrons? Square Planar Complexes Ligands in Organometallic Chemistry Carbonyl (CO) Complexes Ligands Similar to CO 432 IX

7 Dihydrogen Complexes Ligands Having Extended Pi Systems Bonding Between Metal Atoms and Organic Pi Systems Linear Pi Systems Cyclic Pi Systems Complexes Containing Metal-Carbon Sigma Bonds Alkyl Complexes Carbene (Alkylidene) Complexes Carbyne (Alkylidyne) Complexes Spectral Analysis and Characterization of Organometallic Complexes Infrared Spectra NMR Spectra Examples of Characterization ORGANOMETALLIC REACTIONS AND CATALYSIS Reactions Involving Gain or Loss of Ligands Ligand Dissociation and Substitution Oxidative Addition Reactions Reductive Elimination Nucleophilic Displacement Reactions Reactions Involving Modification of Ligands Insertion Reactions Carbonyl Insertion (Alkyl Migration) Reactions Hydride Elimination Reactions Abstraction Organometallic Catalysts Catalytic Deuteration Hydroformylation Monsanto Acetic Acid Process Wacker (Smidt) Process Hydrogenation by Wilkinson's Catalyst Olefin Metathesis Heterogeneous Catalysts Ziegler-Natta Polymerizations Water Gas Reaction PARALLELS BETWEEN MAIN GROUP AND ORGANOMETALLIC CHEMISTRY Main Group Parallels with Binary Carbonyl Complexes The Isobai Analogy Extensions of the Analogy Examples of Applications of the Analogy Cluster Compounds Boranes Heteroboranes Metallaboranes and Metallacarboranes Carbonyl Clusters Carbide Clusters Metal-Metal Bonds in Cluster Compounds Metal-Metal Bonds Additional Comments on Clusters 531 X

8 1 5 BIOINORGANIC AND ENVIRONMENTAL CHEMISTRY Porphyrins and Related Complexes Iron Porphyrins Similar Ring Compounds Other Iron Compounds Potassium and Sodium Zinc and Copper Enzymes Nitrogen Fixation Environmental Chemistry Metals Nonmetals 555 APPENDIX A ANSWERS TO EXERCISES 562 APPENDIX B-1 IONIC RADII 586 APPENDIX B-2 IONIZATION ENERGY 589 APPENDIX B-3 ELECTRON AFFINITY 590 APPENDIX B-4 PAULING ELECTRONEGATMTIES 591 APPENDIX C CHARACTER TABLES 592 APPENDIX D ELECTRON-DOT DIAGRAMS AND FORMAL CHARGE 602 INDEX 609 Xl

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