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

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1 Inorganic Chemistry Second Edition GARY L. MIESSLER DONALD A. TARR St. Olaf College Northfield, Minnesota Prentice Hall, Upper Saddle River, New Jersey 07458

Contents PREFACE xiii INTRODUCTION TO INORGANIC CHEMISTRY 1 1-1 What is Inorganic Chemistry?

2 Contents PREFACE xiii INTRODUCTION TO INORGANIC CHEMISTRY What is Inorganic Chemistry? Contrasts with Organic Chemistry Genesis of the Elements (The Big Bang) and Formation of the Earth Nuclear Reactions and Radioactivity The History of Inorganic Chemistry 10 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 Quantum Numbers and Atomic Wave Functions The Aufbau Principle Shielding Periodic Properties of Atoms Ionization Energy Electron Affinity Covalent and lonic Radii 42 SIMPLE BONDING THEORY Lewis Electron-Dot Diagrams Expanded Shells Resonance Electronegativity and Bond Polarity Formal Charge Formal Charge and Expanded Shells Multiple Bonds in Be and B Compounds Valence Shell Electron Pair Repulsion Theory Lone Pair Repulsion Multiple Bonds Electronegativity 62 v

3 3-4 Polar Bonds Hydrogen Bonding 66 4 SYMMETRY AND GROUP THEORY Symmetry Elements and Operations Point Croups Properties and Representations of Groups Matrices Representations of Point Groups Character Tables Examples and Applications of Symmetry Chirality Molecular Vibrations 97 5 MOLECULAR ORBITALS Formation of Molecular Orbitals from s and p Orbitals Bonding in H Molecular Orbitals from p Orbitals Homonuclear Diatomic Molecules Molecular Orbitals Orbital Mixing Homonuclear Diatomic Molecules Photoelectron Spectroscopy Correlation Diagrams Molecular Orbitals from d Orbitals Heteronuclear Diatomic Molecules Polar Bonds lonic Compounds and Molecular Orbitals Molecular Orbitals for Larger Molecules FHF C The Group Theoretical Approach to Bonding H NH BF Hybrid Orbitals Expanded Shells and Molecular Orbitals ACID-BASE AND DONOR-ACCEPTOR CHEMISTRY 6-1 Acid-Base Concepts as Organizing Concepts History Arrhenius Concept Brönsted-Lowry Concept Solvent System Concept Lewis Concept Other Definitions Acid and Base Strength Measurement of Acid-Base Interactions Thermodynamic Measurements Proton Affinity Acidity and Basicity of Binary Hydrogen Compounds Inductive Effects 163

Contents VII 6-3-6 Strength of Oxyacids 164 6-3-7 Acidity of Cations in Aqueous Solution 165 6-3-8 Steric Effects 166 6-3-9 Solvation and Acid Base Strength 168 6-3-10 Nonaqueous Solvents and

4 Contents VII Strength of Oxyacids Acidity of Cations in Aqueous Solution Steric Effects Solvation and Acid Base Strength Nonaqueous Solvents and Acid-Base Strength Superacids Hard and Soft Acids and Bases Theory ofhard and Soft Acids and Bases Quantitative Measures Frontier Orbitals and Acid-Base Reactions Carbon Monoxide Hydrogen Bonding 186 THE CRYSTALLINE SOLID STATE Formulas and Structures Simple Structures Structures of Binary Compounds More Complex Compounds Radius Ratio Thermodynamics of Ionic Crystal Formation Lattice Enthalpy and Madelung Constant Solubüity, Ion Size (Large-large and Small-small), and HSAB Molecular Orbitals and Band Structure Diodes, the Photovoltaic Effect, and Light-Emitting Diodes Superconductivity Low-Temperature Superconductivity Alloys The Theory of Superconductivity (Cooper Pairs) High-Temperature Superconductors (YBa 2 Cu and Related Compounds) Bonding in Ionic Crystals Imperfections in Solids Silicates 219 CHEMISTRY 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 ofthe Group 13 (IIIA) Elements 242

VÜi Contents 8-6 Group 14 (IVA) 245 8-6-1 The Elements 245 8-6-2 Compounds 249 8-7 Group 15 (VA) 253 8-7-1 The Elements 254 8-7-2 Compounds 255 8-8 Group 16 (VIA) 259 8-8-1 The Elements 259 8-9 Group

5 VÜi Contents 8-6 Group 14 (IVA) The Elements Compounds Group 15 (VA) The Elements Compounds Group 16 (VIA) The Elements Group 17 (VIIA): The Halogens The Elements Group 18 (VIIIA): The Noble Gases The Elements Chemistry COORDINATION CHEMISTRY I: STRUCTURES AND ISOMERS History Nomenclature Isomerism Stereoisomerism Eour-Coordinate Complexes Chirality Six-Coordinate Octahedral Complexes Combinations of Chelate Rings Ligand Ring Conformation Experimental Separation and Identification oflsomers Hydrate Isomerism Coordination Isomerism Linkage (Ambidentate) Isomerism Coordination Numbers and Structures Low Coordination Numbers (CN=1, 2, and 3) Coordination Number Coordination Number Coordination Number Coordination Number Coordination Number Larger Coordination Numbers COORDINATION CHEMISTRY II: BONDING Experimental Evidence for Electronic Structures Thermodynamic Data Magnetic Susceptibility Electronic Spectra Coordination Numbers and Molecular Shapes Theories of Electronic Structure Valence Bond Theory Crystal Field Theory Ligand Field Theory Molecular Orbitals for Octahedral Complexes Orbital Splitting and Electron Spin Ligand Field Stabilization Energy Pi Bonding 326

6 Contents Square-Planar Complexes Tetrahedral Complexes Angular Overlap Sigma Donor Interactions Pi Acceptor Interactions Pi Donor Interactions Magnitudes ofe a, e n, and A Types ofligands and the Spectrochemical Series The Jahn-Teller Effect Four- and Six-Coordinate Preferences OtherShapes 348 COORDINATION CHEMISTRY IM: ELECTRONIC SPECTRA Absorption of Light Beer-Lambert Absorption Law Quantum Numbers of Multielectron Atoms Spin-Orbit Coupling Electronic Spectra of Coordination Compounds Selection Rules Correlation Diagrams Tanabe-Sugano Diagrams Jahn-Teller Distortions and Spectra Examples of Applications of Tanabe-Sugano Diagrams: Determining A o from Spectra Tetrahedral Complexes Charge-Transfer Spectra 379 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 Kinetic Chelate Effect Stereochemistry of Reactions Substitution in trans Complexes Substitution in eis Complexes Isomerization of Chelate Rings Substitution Reactions of Square-Planar Complexes Kinetics and Stereochemistry of Square-Planar Substitutions Evidence for Associative Reactions 404

7 12-7 The trans Effect Explanations ofthe trans Effect Oxidation-Reduction Reactions Inner- and Outer-Sphere Reactions Conditions for High and Low Oxidation Numbers Reactions of Coordinated Ligands Hydrolysis of Esters, Amides, and Peptides Template Reactions Electrophilic Substitution 418 ORGANOMETALLIC CHEMISTRY Historical Background Organic Ligands and Nomenclature The 18-ElectronRule Counting Electrons Why 18 Electrons? Square-Planar Complexes Ligands in Organometallic Chemistry Carbonyl (CO) Complexes Ligands Similar to CO Hydride and Dihydrogen Complexes Ligands Having Extended Pi Systems Bonding Between Metal Atoms and Organic Pi Systems Linear Pi Systems Cyclic Pi Systems Füllerene Complexes Complexes Containing M C, M=C, and M=C Bonds Alkyl and Related Complexes Carbene Complexes Carbyne (Alkylidyne) Complexes Spectral Analysis and Characterization of Organometallic Complexes Infrared Spectra NMR Spectra Examples of Characterization 475 ORGANOMETALLIC REACTIONS AND CATALYSIS Reactions Involving Gain or Loss of Ligands Ligand Dissociation and Substitution Oxidative Addition Reductive Elimination Nucleophilic Displacement Reactions Involving Modification of Ligands Insertion Carbonyl Insertion (Alkyl Migration) ,2 Insertions Hydride Elimination Abstraction Organometallic Catalysts An Example of Catalysis: Catalytic Deuteration Hydroformylation Monsanto Acetic Acid Process Wacker (Smidt) Process 504

Contents XI 14-3-5 Hydrogenation by Wilkinson 's Catalyst 505 14-3-6 Olefin Metathesis 505 14-4 Heterogeneous Catalysts 509 14-4-1 Ziegler-Natta Polymerizations 510 14-4-2 Water Gas Reaction 511 15

8 Contents XI 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 Isolobal Analogy Extensions of the Analogy Examples of Applications of the Analogy Metal-Metal Bonds Multiple Metal-Metal Bonds Cluster Compounds Boranes Heteroboranes Metallaboranes and Metallacarboranes Carbonyl Clusters Carbide Clusters Additional Comments on Clusters BIOINORGANIC AND ENVIRONMENTAL CHEMISTRY Porphyrins and Related Complexes hon Porphyrins Similar Ring Compounds Other Iron Compounds Zinc and Copper Enzymes Nitrogen Fixation Nitric Oxide Inorganic Medicinal Compounds Cisplatin and Related Complexes Auranofin and Arthritis Treatment Environmental Chemistry Metals Nonmetals 574 APPENDIX A ANSWERS TO EXERCISES 582 APPENDIX B-1 IONICRADM 612 APPENIDX B-2 IONIZATION ENERGY 615 APPENDIX B-3 ELECTRON AFFINITY 616 APPENDIX B-4 PAULING ELECTRONEGATIVITIES 617 APPENDIX B-5 ABSOLUTE HARDNESS PARAMETERS 618 APPENDIX B-6 C A, E A, C ß/ AND ß VALUES 620 APPENDIX C CHARACTER TABLES 621 APPENDIX D ELECTRON-DOT DIAGRAMS AND FORMAL CHARGE 631 INDEX 636

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

Inorganic Chemistry GARY L. MIESSLER DONALD A. TARR St. Olaf College Northfield, Minnesota Contents PREFACE xiii 1 INTRODUCTION TO INORGANIC CHEMISTRY 1 1-1 What Is Inorganic Chemistry? 1 1-2 Contrasts