ELEMENTARY INORGANIC CHEMISTRY
1 Atoms and Electrons 1 11 Introduction 1 12 The Bohr Atom 2 13 Electron as a Wave 5 14 The Schrödinger Equation 6 141 Schrödinger Equation Solution for One-Electron Systems 7 15 Quantum Numbers 8 16 Orbital Representations 9 161 Two-Dimensional Representations 9 162 Three-Dimensional Representations 12 17 Multi-Electron Atoms 12 171 Putting Electrons into Atomic Orbitals 12 172 Exceptions to Madelung’s Rule 15 2 The Periodic Table 19 21 Early Development 19 22 Structure of the Periodic Table 21 23 Periodic Trends of Some Physical Properties of Atoms 23 231 Ionization Energy 23 232 Electron Affinity 27 233 Electronegativity 29 234 Covalent, Ionic, or Metallic Bonding, and Electronegativity 31 235 Atom Size 34 236 Bond Valence Model 37 237 Ionic Radii 39 238 Periodic Trends in Atom Sizes 39 24 Summary of Periodic Trends 39 25 Supporting Information 41 3 Covalent Bonding Theories 45 31 Introduction 45 311 Common Terms 46 32 Lewis Electron Dot Theory 47 321 Electron Dot Diagrams 48 322 Expanded Octet 49 323 Nonequivalent Resonance Structures, Formal Charge, and the Octet Rule 49 324 Problems for the Octet Rule 51 325 Lewis Structures and Oxidation States 51 33 Valence Shell Electron Pair Repulsion, VSEPR, Theory 53 331 Geometrical Arrangements from VSEPR Theory 53 332 Structural Trends and VSEPR Theory 55 333 Problems with VSEPR Theory 56 34 Valence Bond Theory 57 341 Hybridization of Orbitals 57 342 Multiple Bonds and Resonance 59 343 Hybridization of d Orbitals 60 344 Summary of Problems and Advances 62 35 Molecular Orbital Theory 64 351 Basics of the Theory 64 352 Molecular Orbitals from p Valence Orbitals in Diatomic Species 67 353 Molecular Orbital Electronic Configurations of Diatomic Species 67 354 Photoelectron Spectroscopy 69 355 Photoelectron Spectra of O2 and N2 70 356 Orbital Mixing in Molecular Orbital Theory 72 357 Molecular Orbitals in Heteronuclear Diatomic Species 74 358 Molecular Orbitals in Triatomic Species 77 359 Molecular Orbitals for Linear and Bent Triatomic Species 78 3510 Trihalide Anions and Related Hypervalent Species 82 3511 Methane 87 36 Putting It All Together 88 37 Supporting Information 89 371 Secular Equation Solution for a Homonuclear Triatomic System 89 4 Energy 93 41 Introduction 93 411 Basic Thermodynamic Relationships 93 412 Gibbs Free Energy and the Equilibrium Constant 96 42 Bond Energies and Bond Dissociation Enthalpies 100 421 Average Bond Dissociation Enthalpies 100 422 Applications of Bond Dissociation Enthalpies 102 423 Bond Dissociation Enthalpies and Bonding Theory 105 43 Thermodynamics and Chemical Cycles 107 431 Process Chemical Cycles 107 432 Isothermal Chemical Cycles 110 433 Lattice Energies and Interionic Distances 112 434 Lattice Energies and Molecular Volumes 114 435 Other Isothermal Cycles 117 5 Acids and Bases 125 51 Introduction 125 52 Brønsted or Protic Acids and Bases 125 521 Characteristics of Brønsted Acids and Bases 125 522 Strengths of Brønsted Acids and Bases 128 523 Strengths of Strong Brønsted Acids 131 524 Brønsted Superacids 134 525 Brønsted Superbases 137 53 Lewis Acids and Bases 139 531 Strengths of Lewis Acids and Bases 142 532 Single Reference Scales of Acidity and Basicity 142 533 The Dual Parameter E and C Model for Lewis Acidity and Basicity 143 534 Some General Trends in Lewis Acidities 145 535 The Hard and Soft Model for Lewis Acidity and Basicity 147 536 Frustrated Lewis Pairs, FLPs 152 6 Reaction Types and Mechanisms 157 61 Introduction 157 62 Reaction Types 157 621 Proton-Transfer Reactions 157 622 Substitution Reactions 158 623 Oxidation–Reduction Reactions 158 624 Oxidative-Addition Reactions 158 625 Isomerization Reactions 159 63 Kinetic Background 160 631 The Rate Law 160 632 Temperature and Pressure Effects 162 633 Ionic Strength Effects 163 64 Proton-Transfer Mechanisms 163 65 Substitution Reaction Mechanisms 165 66 Oxidation–Reduction Reaction Mechanisms 174 661 Reaction Types 174 662 Inner-Sphere Electron Transfer 175 663 Outer-Sphere Electron Transfer 178 67 Oxidative-Addition Reaction Mechanisms 180 671 Oxidative Addition of X–Y Molecules 180 672 Oxidative Addition of Organic Halides to Transition Metals 181 68 Isomerization Reaction Mechanisms 184 681 Linkage Isomerization 184 682 Geometrical Isomerization 189 69 Supporting Information 192 691 Rate Laws 192 692 Rapid-Equilibrium Assumption 192 693 Steady-State Assumption 193 7 The Solid State and Symmetry 197 71 Introduction 197 72 Some Elements of Group Theory 197 721 Symmetry Operations and Point Groups 198 722 Group Theory and Vibrational Spectroscopy 201 723 Selection Rules in Vibrational Spectroscopy 204 724 Group Theory and Orbitals 205 73 Crystalline Inorganic Solids 208 731 Introduction 208 732 Some Common Structure Types 208 733 Radius-Ratio Method 214 734 Polymorphs and Polytypes 216 74 Metals 218 741 Properties of Metals 218 742 Structures of Metals 218 743 Bonding in Metals 221 75 Electrical Insulators and Semiconductors 224 76 Spinels and Perovskites 226 761 Structures of Spinels 226 762 Structures of Perovskites 229 77 Supporting Information 233 771 Crystal Structures: Seeing the Picture 233 772 Ionic Radii 236 8 Introduction to Transition Metals 239 81 Introduction 239 82 Coordination Compounds 240 83 Ligand Types in Coordination Compounds 242 84 Ligand Arrangements and Isomers 245 841 Octahedral, Square Planar, and Tetrahedral Systems 246 842 Other Ligand Arrangements 247 843 Ionization Isomers 250 844 Hydrate Isomers 250 845 Optical Isomers 250 846 Meso Isomers 255 847 Isomer Identification and Counting 256 848 Conformational Isomers 257 849 Isomers as Templates for Open-Framework Materials 258 85 Bonding Theories for Transition-Metal Complexes 258 851 Historical Background 258 852 Crystal Field Theory 259 853 Valence Bond Theory 262 854 Ligand Field Theory 264 86 Electronic Spectra: Colors 267 861 Electronic States and Term Symbols 268 862 Electronic States in an Octahedral Field 273 863 Energy Units in Electronic Spectroscopy 275 864 Energies of Russell–Saunders Terms and Ligand Field States 275 865 Electronic Spectra of d3 and d8 Systems 278 866 Electronic Spectra of d6 Systems 281 87 Trends in Values of D and B 284 88 Six-Coordinate Complexes of Lower Symmetry than Oh 286 89 Magnetic Properties 289 891 Basic Concepts and Terminology 289 892 Magnetic Moment and Unpaired Electrons 290 893 Representative Examples of Magnetic Behavior 293 9 The Transition Metals: Groups 3–12 301 91 Introduction: The Elements 301 92 General Properties of the Transition Metals 302 93 Group 3: Scandium, Yttrium, and Lanthanum 305 94 Group 4: Titanium, Zirconium, and Hafnium 308 95 Group 5: Vanadium, Niobium, and Tantalum 311 96 Group 6: Chromium, Molybdenum, and Tungsten 316 97 Group 7: Manganese, Technetium, and Rhenium 323 98 Group 8: Iron, Ruthenium, and Osmium 328 99 Group 9: Cobalt, Rhodium, and Iridium 340 910 Group 10: Nickel, Palladium, and Platinum 347 911 Group 11: Copper, Silver, and Gold 354 912 Group 12: Zinc, Cadmium, and Mercury 365 10 Organometallic Chemistry of Transition Metals 375 101 What Is Organometallic? 375 102 Bonding in Organometallic Systems 378 1021 The Eighteen-Electron “Rule” 379 1022 Arrangement of Organometallic Substituents 385 1023 Bonding in Metal Carbonyls 388 1024 Bonding in Metal Bis-Cyclopentadiene Species 392 103 Reactions of Organometallic Species 397 11 The Lanthanides 407 111 Introduction 407 112 Extraction and Separation of the Lanthanides 408 113 The Elements 411 114 The Lanthanide Contraction 414 115 Compounds of the Lanthanides 416 1151 Oxides of the Lanthanides 416 1152 Halides of the Lanthanides 420 1153 Organometallic Lanthanides 426 12 Groups 1 and 2 437 121 Introduction: The Elements 437 122 Natural Sources and Preparation of the Elements 440 1221 Hydrogen 440 1222 Lithium 445 1223 Sodium 446 1224 Potassium, Rubidium, and Cesium 447 1225 Beryllium 448 1226 Magnesium 448 1227 Calcium 449 1228 Strontium and Barium 449 123 Structures, Properties, and Uses of the Elements 450 1231 Hydrogen 451 1232 The Alkali Metals 452 1233 The Alkaline Earth Metals 463 124 Binary Compounds with Oxygen 468 1241 The Oxide and Peroxide of Hydrogen 468 1242 Oxides of the Alkali Metals 471 1243 Oxides of the Alkaline Earth Metals 473 1244 Peroxides of the Alkali and Alkaline Earth Metals 475 1245 Superoxides of the Alkali Metals 477 1246 Ozonides of the Alkali Metals 479 125 Aqueous Ions 480 1251 The Hydrated Proton 480 1252 Aqueous Cations 481 1253 Aqueous Anions 482 126 Binary Carbides of the Metals of Groups 1 and 2 483 127 Binary Nitrides of the Metals of Groups 1 and 2 487 13 Group 13 495 131 Introduction: The Elements 495 132 Natural Sources and Preparation of the Elements 496 1321 Boron 496 1322 Aluminum 497 1323 Gallium, Indium, and Thallium 498 133 Structures, Properties, and Uses of the Elements 498 1331 Boron 498 1332 Aluminum 500 1333 Gallium, Indium, and Thallium 501 134 Oxides 502 1341 General Features 502 1342 Boron Oxides 502 1343 Aluminum Oxides 503 1344 Gallium and Indium Oxides 505 1345 Thallium Oxides 507 135 Borates, Boric Acid, and Their Derivatives 508 1351 Borate Anion Structures 508 1352 Boric Acid and Metaboric Acid Structures 509 1353 Boric Acid and Its Esters in Aqueous Solution 510 1354 Boronic Acids 513 136 Aluminum, Gallium, and Indium Hydroxides and Aqua Ions 516 1361 Aluminum Hydroxide 516 1362 Aqueous Al(III) 517 1363 Gallium and Indium Hydroxides and Aqua Ions 519 137 Borides 520 138 Nitrides 521 1381 Boron Nitride 521 1382 Aluminum Nitride 522 1383 Gallium Nitride 523 1384 Indium Nitride 523 139 Carbides 524 1391 Boron Carbide 524 1392 Aluminum Carbide 524 1310 Hydrides 524 13101 Tetrahydride Anions of Boron and Aluminum 525 13102 Boron Hydrides 528 13103 Boron Hydride Derivatives 533 13104 Carboranes 538 13105 Metallacarboranes 540 13106 Aluminum Hydride 544 1311 Halides 545 13111 Properties and Structures 545 13112 Trihalides as Lewis Acids 548 1312 Organic Derivatives 550 13121 Properties and Structures 550 13122 Activators for Olefin Polymerization 552 13123 Fluorinated Organoboron Derivatives 553 13124 Organoboron Derivatives in Hydroboration and C–C Bond Formation 554 14 Group 14 559 141 Introduction: The Elements 559 142 Natural Sources and Preparation of the Elements 561 1421 Carbon 561 1422 Silicon 562 1423 Germanium 563 1424 Tin 563 1425 Lead 564 143 Structures, Properties, and Uses of the Elements 565 1431 Common Allotropes of Carbon 565 1432 Fullerenes 567 1433 Carbon Nanotubes 567 1434 Graphene 571 1435 Silicon 574 1436 Germanium 577 1437 Tin 577 1438 Lead 579 144 Oxides 581 1441 The Gaseous Monoxides 581 1442 The Solid Monoxides 582 1443 Carbon Dioxide, CO2 585 1444 Silicon Dioxide or Silica, SiO2 588 1445 Germanium Dioxide, GeO2 592 1446 The Oxides of Tin(IV) and Lead(IV) 592 145 Oxoacids, Oxanions, and Aqueous Cations 596 1451 Carbon Oxoacids and Oxoanions 596 1452 Silicon Oxoacids and Oxoanions 603 1453 Germanium Oxoacids and Oxoanions 609 1454 Tin and Lead Aqua Cations and Oxoanions 611 146 Halides 615 1461 The Tetrahalides 615 1462 The Dihalides 621 1463 Lewis Base Adducts of Group 14 Halides 626 147 Organic Derivatives of Si, Ge, Sn, and Pb 632 148 Silicones 637 149 Catenation 639 1491 Catenation with Single Bonds 639 1492 Catenation with Double Bonds 642 1493 Catenation with Triple Bonds 645 1410 Amines and Nitrides 648 14101 Amines 648 14102 Nitrides 651 15 Group 15 661 151 Introduction: The Elements 661 152 Natural Sources and Preparation of the Elements 663 1521 Nitrogen 663 1522 Phosphorus 663 1523 Arsenic, Antimony, and Bismuth 663 153 Structures, Properties, and Uses of the Elements 664 1531 Dinitrogen or Nitrogen 664 1532 Phosphorus 669 1533 Arsenic, Antimony, and Bismuth 674 154 Oxides 676 1541 Oxides of Nitrogen 676 1542 Oxides of Phosphorus 682 1543 Oxides of Arsenic, Antimony, and Bismuth 684 155 Oxoacids and Oxoanions 687 156 Hydrides 698 1561 The AH3 Hydrides: Properties and Structures 698 1562 Ammonia 698 1563 Hydrazine 701 1564 Diazene 704 1565 Hydroxylamine 705 1566 Nitroxyl 708 1567 Hydrides of Phosphorus, Arsenic, Antimony, and Bismuth 710 157 Halides 711 1571 The Trihalides, AX3 711 1572 The Pentahalides, AX5 715 1573 The Oxohalides, OAX3 718 1574 Mixed Halides of Phosphorus: Halogen Exchange 721 1575 Phosphorus(III) Halide Derivatives: Phosphenium Ions 722 158 Binary Nitrides 723 1581 Classification of Nitrides 723 1582 Preparations and Uses of Some Nitrides 724 1583 Structures of Representative Nitrides 725 159 Organic Amines, Phosphanes, and Related Compounds 726 1591 Organic Derivatives of the AL3 Type 727 1592 Organic Derivatives of the AL5 Type 728 1593 Preparations and Uses of Some Organic Amines and Phosphanes 731 1594 Phosphanes as Ligands in Organometallic Chemistry 733 16 Group 16 739 161 Introduction: The Elements 739 162 Natural Sources and Preparation of the Elements 740 1621 Oxygen 740 1622 Sulfur 740 1623 Selenium and Tellurium 742 163 Structures, Properties, and Uses of the Elements 742 1631 Dioxygen or Oxygen 742 1632 Singlet Oxygen 743 1633 Ozone and Covalent Ozonides 746 1634 Sulfur 749 1635 Selenium, Tellurium, and Polonium 750 164 Oxides, Oxoacids, and Oxoanions 751 1641 Oxoanions of Oxygen 751 1642 Oxides, Oxoacids, and Oxoanions of Sulfur 753 1643 Oxides, Oxoacids, and Oxoanions of Selenium and Tellurium 763 165 Halides and Oxohalides 764 166 Hydrides 770 167 Nitrides of Sulfur 771 168 Organic Derivatives 773 17 Group 17 777 171 Introduction: The Elements 777 172 Natural Sources and Preparation of the Elements 779 1721 Fluorine 779 1722 Chlorine 779 1723 Bromine 780 1724 Iodine 780 173 Structures, Properties, and Uses of the Elements 781 174 Oxides, Oxoacids, and Oxoanions 783 1741 Oxygen Halides, Hypohalous Acids, and Hypohalites 783 1742 The Halogen Dioxides 788 1743 The Halites and Halous Acids 791 1744 The Halates and Halic Acids 792 1745 The Perhalates and Perhalic Acids 795 175 Polyhalogens and Polyinterhalogens 797 1751 Properties of Some Polyhalogens and Polyinterhalogens 797 1752 Structures of Some Polyhalogens and Polyinterhalogens 800 18 Group 18 805 181 Introduction: The Elements 805 182 Natural Sources and Preparation of the Elements 807 1821 Helium 807 1822 Neon, Argon, Kryton, and Xenon 807 183 Structures, Properties, and Uses of the Elements 808 1831 Helium 808 1832 Neon, Argon, Krypton, and Xenon 808 184 Chemical Derivatives of the Noble Gases 810 1841 Binary Fluorides of Xenon and Krypton 810 1842 Binary Oxides and Oxoanions of Xenon 817 1843 Oxofluorides of Xenon 819 1844 Species Formed by Argon 821 19 Bioinorganic Chemistry 823 191 Introduction 823 192 Functions of Some Main Group Elements 824 1921 Iodine and Selenium 825 193 Functions of Some Transition Metals 828 1931 Zinc in Human Carbonic Anhydrase, hCA II 828 1932 Zinc in Peptidases 830 1933 Cobalt in Coenzyme B12