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Concepts and Models of Inorganic Chemistry Third Edition Bodie E. Douglas Universily of Pittsburgh Darl H. McDaniel University of Cincinnati John J. Alexander University of Cincinnati John Wiley & Sons, Inc. New York Chichester Brisbane Toronto Singapore Contents PART I Some Basic Concepts \ CHAPTER 1 Atomic Structure and the Periodic Table 3 1.1 Models in Chemistry 1.2 Historical Background 3 5 1.3 Atomic Structure and the Basis of the Periodic Table 1.4 Spectroscopic Terms and the Zeeman Effect; One-Electron Atoms 8 32 1.5 1.6 1.7 1.8 34 42 46 47 50 51 The Vector Model and Term Structure for Polyelectron Atoms Ionization Energies Electron Afflnities Absolute Electronegativity and Absolute Hardness General References Problems CHAPTER 2 Molecular Models 54 2.1 Review of Covalent Bonding 2.2 Valence Bond (Pauling-Slater) Theory 54 66 xi xii Contents 2.3 Shapes of Molecules 2.4 Electronegativity 2.5 Radii of Atoms in Covalent Compounds 2.6 The Hydrogen Bond 2.7 Weak Interactions in Covalent Substances General References Problems 72 82 88 92 99 102 102 CHAPTER 3 Symmetry 105 3.1 3.2 3.3 3.4 3.5 Introduction Symmetry Elements and Symmetry Operations Introduction to Groups Symmetry Point Groups Class Structure, Representations, and Character Tables 105 106 114 116 127 3.6 Chemical Applications of Symmetry 3.7 Summary of Terminology and Notation from Symmetry and Group Theory General References Appendix 3.1 Matrix Representation of Transformation a n d Matrix Multiplication Appendix 3.2 The Direct Product of Representations Problems 138 l4l 144 144 147 147 PART II Bonding and Structure 149 CHAPTER 4 Discrete Molecules: Molecular Orbitals 151 4.1 Diatomic Molecules 151 4.2 Linnett's Double Quartet 4.3 Triatomic Molecules 4.4 Xenon Difluoride 163 166 176 4.5 4.6 4.7 4.8 177 185 188 193 196 196 Boron Trifluoride—A Group Theoretical Treatment Diborane Cyclic-Planar IT Molecules Basis Sets and Frontier Orbitals General References Problems Contents CHAPTER 5 Inorganic Solids: lonic Models xiii 198 5.1 Simple lonic Solids 199 5.2 5.3 5.4 5.5 5.6 204 206 211 212 220 Close Packing lonic Struetures Based lipon Close-Packed Arrangements Radius Katios f'or Stable Arrangements in lonic Crystals Common Struetures of lonic Crystals Notation for Struetures Based Upon Close Packing 5.7 lonic Kadii 5.8 5.9 5.10 5.11 5.12 Lattice Energy Solubilities of lonic Substances Giant Molecules Struetures of Silicates Crystal Struetures of Metals General References Problems 221 224 235 238 239 246 248 249 CHAPTER 6 Solid-State Chemistry 251 6.1 Crystal Structure 6.2 Defect Struetures 251 264 6.3 6.4 6.5 6.6 6.7 268 284 292 294 295 Electronic Structure of Solids Graphite as a Two-Uimensional Solid Metals. Insulators, and Semiconductors Some Liniitations and Lxtensions of the Simple Band Theory Superconductivity 6.8 Buckminsterfullerene General References Problems 300 303 304 PART III Chemical Reactions 307 CHAPTER 7 Acids and Bases 309 7.1 Models of Acids and Bases 7.2 Protonic Acids 7.3 Acid—Base Behavior of the Binary Oxides and Aqua Cations 309 313 326 xiv Contents 7.4 Nonprotonic Concepts of Acid-Base Reactions 7.5 The Drago-Wayland Equation 7.6 Solid Acids General References Problems 333 343 346 347 347 CHAPTER 8 Oxidation—Reduction Reactions 350 8.1 Conventions Covering Standard States 8.2 Methods of Determining Changes in Free Energy 350 352 8.3 Schematic Representation of Galvanic Cells 353 8.4 8.5 8.6 8.7 8.8 354 356 363 366 368 Conventions Regarding Cells Calculations Using emf Data Pourbaix (or Predominance Area) Diagrams Geochemistry of Manganese Periodic Trends among the Transition Elements 8.9 Some Redox Reactions of Nonmetals 8.10 Equilibrium Constants from emf Data General References Problems 370 372 373 373 PART IV Coordination Chemistry 377 CHAPTER 9 Models and Stereochemistry 379 9.1 Introduction 9.2 Analytical Applications 9.3 Brief Summarv of Nomenclature of Coordination Compounds 379 381 383 9.4 Stabilities of Coordination Compounds 9.5 Werner's Coordination Theory 384 390 9.6 Valence Bond Models 9.7 Simple Electrostatic Models of Bonding 9.8 The Ligand-Field Theory 392 398 401 Contents 9.9 9.10 9.11 9.12 9.13 9.14 XV Isomerism of Coordination Compounds Coordination Number Four Coordination Number Six Coordination Number Five Lower Coordination Numbers Higher Coordination Numbers 411 413 415 424 427 428 9.15 Stereochemically Nonrigid and Fluxional Molecules General References Problems 432 437 438 CHAPTER 10 Spectra and Bonding 441 10.1 Introduction 441 10.2 10.3 10.4 10.5 Ligand-Field Spectra of Octahedral Complexes Complexes of Lower Symmetry Charge Transfer Bands Circular üichroism and Optica! Rotatory Dispersion 442 459 463 465 10.6 10.7 10.8 10.9 Pictorial Molecular-Orbital Description of Bonding Effects of TT Bonding Group Theoretical Treatment Comparison of the Oifferent Approaches to Bonding in Coordination Compounds General References Problems 468 471 472 478 478 479 CHAPTER 11 Reaction Mechanisms 482 11.1 11.2 11.3 11.4 11.5 482 486 487 517 519 The Kinetic Model Introduction to Ligand Substitution Reactions Octahedral Complexes: Ligand Substitution Reactions Racemization Reactions Square-Planar Complexes: Ligand Substitution Reactions 11.6 Catalysis of Substitution by Redox Processes 11.7 Redox Reactions 528 528 11.8 Photochemical Reactions General References Problems 543 549 549 ) Contents PART V Organometallic Chemistry 559 CHAPTER 12 General Principles 561 12.1 Introduction 12.2 Carbonyl Complexes 12.3 Bonding of Organic Ligands to Metals 562 562 577 12.4 Experimental Eviderice t'or Back-Üonation 12.5 Structural Characterization of Organometallic Compounds 597 603 12.6 The Isolobal Analogy 12.7 Dihydrogen Complexes General References Problems 605 606 609 609 CHAPTER 13 Survey of Organometallic Compounds 614 13.1 Some Chemistry of Olefin Complexes 614 13.2 Alkyne Complexes 615 13.3 Allyl Complexes 13.4 Butadiene Complexes 619 622 13.5 Cyclic TT Complexes 13.6 Compounds with Metal—Carbon a Bonds 13.7 Compounds with Multiple Metal-Carbon Bonds General References Problems 626 635 646 650 650 CHAPTER 14 Organometallic Reactions, Mechanisms, and Catalysis 653 14.1 Fundamental Reactions 14.2 Homogeneous Catalysis by Soluble Transition Metal Complexes General References Problems 653 685 697 697 xvii Contents PART VI Selected Topics 703 CHAPTER 15 Chemistry and Periodic Trends among Metals 705 15.1 General Periodic Trends among Metals 15.2 Group 1 (IA)—The Alkali Metals 705 708 15.3 Group 2 (IIA)—The Alkaline Earth Metals 15.4 Group 11 (IB)—The Goinage Metals 718 724 15.5 15.6 15.7 15.8 15.9 15.10 Group 12 (IIB)—The Zinc Subgroup Group .3 (IIIA)—The Scandium Family and Rare Earths The Actinide Metals Transition Metals, Groups 4 - 7 (IVA-VIIA) Groups 8, 9. and 10 (Group VIII) Compounds Containing Metal-Metal Bonds 729 732 737 738 747 751 General References 757 Problems 757 CHAPTER 16 Chemistry of Some Nonmetals 760 16.1 16.2 16.3 16.4 760 761 773 789 General Periodic Trends for Nonmetals Nitrogen and Phosphorus Oxygen, Sulfur, and Selenium The Halogens 16.5 The Noble Gases General References Problems 807 812 813 CHAPTER 17 Cluster and Cage Compounds 816 17.1 Introduction 816 17.2 The Bonding Problem in Boranes 819 17.3 17.4 17.5 17.6 823 826 832 834 Structures of the Boron Hydrides Molecular Orbital Description of Bonding in Boron Hydrides Heteroboranes Chemistry of the Boranes xviii Contents 17.7 17.8 17.9 17.10 Synthesis of Boron Hydrides Carboranes Some Chemistry of Group 13 Cluster Compounds 841 843 847 854 17.11 Electron-Precise Compounds and their Relation to Clusters General References Problems 877 879 880 CHAPTER 18 Bioinorganic Chemistry 888 18.1 Essential Elements 18.2 Oxygen Utilization 888 893 18.3 Supply and Storage of Iron 18.4 Oxidation—Reduction Processes 18.5 Metalloenzymes 901 905 910 18.6 18.7 18.8 18.9 919 922 924 926 927 928 Vitamin Bi 2 Nitrogenase Photosynthesis Roles of Na + , K + , Mg 2+ , Ca 2+ , and Ion Pumps General References Problems APPENDIX A Units AI APPENDIX B Nomenclature of Inorganic Chemistry B-l APPENDIX C Character Tables C-l APPENDIX D Tanabe—Sugano Diagrams Dl APPENDIX E Standard Half-Cell emf Data El INDEX i-i