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 3
1.2 Historical Background 5
1.3 Atomic Structure and the Basis of the Periodic Table 8
1.4 Spectroscopic Terms and the Zeeman Effect; One-Electron Atoms 32
1.5 The Vector Model and Term Structure for Polyelectron Atoms 34
1.6 Ionization Energies 42
1.7 Electron Afflnities 46
1.8 Absolute Electronegativity and Absolute Hardness 47
General References 50
Problems 51

CHAPTER 2
Molecular Models 54
2.1 Review of Covalent Bonding 54
2.2 Valence Bond (Pauling-Slater) Theory 66

xi
xii Contents

2.3 Shapes of Molecules 72

2.4 Electronegativity 82
2.5 Radii of Atoms in Covalent Compounds 88
2.6 The Hydrogen Bond 92
2.7 Weak Interactions in Covalent Substances 99
General References 102
Problems 102

CHAPTER 3
Symmetry 105
3.1 Introduction 105
3.2 Symmetry Elements and Symmetry Operations 106
3.3 Introduction to Groups 114
3.4 Symmetry Point Groups 116
3.5 Class Structure, Representations, and Character Tables 127
3.6 Chemical Applications of Symmetry 138
3.7 Summary of Terminology and Notation from Symmetry and
Group Theory l4l
General References 144
Appendix 3.1 Matrix Representation of Transformation a n d
Matrix Multiplication 144
Appendix 3.2 The Direct Product of Representations 147
Problems 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 163
4.3 Triatomic Molecules 166
4.4 Xenon Difluoride 176
4.5 Boron Trifluoride—A Group Theoretical Treatment 177
4.6 Diborane 185
4.7 Cyclic-Planar IT Molecules 188
4.8 Basis Sets and Frontier Orbitals 193
General References 196
Problems 196
Contents xiii

CHAPTER 5
Inorganic Solids: lonic Models 198
5.1 Simple lonic Solids 199
5.2 Close Packing 204
5.3 lonic Struetures Based lipon Close-Packed Arrangements 206
5.4 Radius Katios f'or Stable Arrangements in lonic Crystals 211
5.5 Common Struetures of lonic Crystals 212
5.6 Notation for Struetures Based Upon Close Packing 220
5.7 lonic Kadii 221
5.8 Lattice Energy 224
5.9 Solubilities of lonic Substances 235
5.10 Giant Molecules 238
5.11 Struetures of Silicates 239
5.12 Crystal Struetures of Metals 246
General References 248
Problems 249

CHAPTER 6
Solid-State Chemistry 251
6.1 Crystal Structure 251
6.2 Defect Struetures 264
6.3 Electronic Structure of Solids 268
6.4 Graphite as a Two-Uimensional Solid 284
6.5 Metals. Insulators, and Semiconductors 292
6.6 Some Liniitations and Lxtensions of the Simple Band Theory 294
6.7 Superconductivity 295
6.8 Buckminsterfullerene 300
General References 303
Problems 304

PART III
Chemical Reactions 307

CHAPTER 7
Acids and Bases 309
7.1 Models of Acids and Bases 309
7.2 Protonic Acids 313
7.3 Acid—Base Behavior of the Binary Oxides and Aqua Cations 326
xiv Contents

7.4 Nonprotonic Concepts of Acid-Base Reactions 333

7.5 The Drago-Wayland Equation 343
7.6 Solid Acids 346
General References 347
Problems 347

CHAPTER 8
Oxidation—Reduction Reactions 350
8.1 Conventions Covering Standard States 350
8.2 Methods of Determining Changes in Free Energy 352
8.3 Schematic Representation of Galvanic Cells 353
8.4 Conventions Regarding Cells 354
8.5 Calculations Using emf Data 356
8.6 Pourbaix (or Predominance Area) Diagrams 363
8.7 Geochemistry of Manganese 366
8.8 Periodic Trends among the Transition Elements 368
8.9 Some Redox Reactions of Nonmetals 370
8.10 Equilibrium Constants from emf Data 372
General References 373
Problems 373

PART IV
Coordination Chemistry 377

CHAPTER 9
Models and Stereochemistry 379
9.1 Introduction 379
9.2 Analytical Applications 381
9.3 Brief Summarv of Nomenclature of Coordination Compounds 383
9.4 Stabilities of Coordination Compounds 384
9.5 Werner's Coordination Theory 390
9.6 Valence Bond Models 392
9.7 Simple Electrostatic Models of Bonding 398
9.8 The Ligand-Field Theory 401
Contents XV

9.9 Isomerism of Coordination Compounds 411

9.10 Coordination Number Four 413
9.11 Coordination Number Six 415
9.12 Coordination Number Five 424
9.13 Lower Coordination Numbers 427
9.14 Higher Coordination Numbers 428
9.15 Stereochemically Nonrigid and Fluxional Molecules 432
General References 437
Problems 438

CHAPTER 10
Spectra and Bonding 441
10.1 Introduction 441
10.2 Ligand-Field Spectra of Octahedral Complexes 442
10.3 Complexes of Lower Symmetry 459
10.4 Charge Transfer Bands 463
10.5 Circular üichroism and Optica! Rotatory Dispersion 465
10.6 Pictorial Molecular-Orbital Description of Bonding 468
10.7 Effects of TT Bonding 471
10.8 Group Theoretical Treatment 472
10.9 Comparison of the Oifferent Approaches to Bonding in
Coordination Compounds 478
General References 478
Problems 479

CHAPTER 11
Reaction Mechanisms 482
11.1 The Kinetic Model 482
11.2 Introduction to Ligand Substitution Reactions 486
11.3 Octahedral Complexes: Ligand Substitution Reactions 487
11.4 Racemization Reactions 517
11.5 Square-Planar Complexes: Ligand Substitution Reactions 519
11.6 Catalysis of Substitution by Redox Processes 528
11.7 Redox Reactions 528
11.8 Photochemical Reactions 543
General References 549
Problems 549
)
Contents

PART V
Organometallic Chemistry 559

CHAPTER 12
General Principles 561
12.1 Introduction 562
12.2 Carbonyl Complexes 562
12.3 Bonding of Organic Ligands to Metals 577
12.4 Experimental Eviderice t'or Back-Üonation 597
12.5 Structural Characterization of Organometallic Compounds 603
12.6 The Isolobal Analogy 605
12.7 Dihydrogen Complexes 606
General References 609
Problems 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 619
13.4 Butadiene Complexes 622
13.5 Cyclic TT Complexes 626
13.6 Compounds with Metal—Carbon a Bonds 635
13.7 Compounds with Multiple Metal-Carbon Bonds 646
General References 650
Problems 650

CHAPTER 14
Organometallic Reactions, Mechanisms, and Catalysis 653
14.1 Fundamental Reactions 653
14.2 Homogeneous Catalysis by Soluble Transition Metal Complexes 685
General References 697
Problems 697
Contents xvii

PART VI
Selected Topics 703

CHAPTER 15
Chemistry and Periodic Trends among Metals 705
15.1 General Periodic Trends among Metals 705
15.2 Group 1 (IA)—The Alkali Metals 708
15.3 Group 2 (IIA)—The Alkaline Earth Metals 718
15.4 Group 11 (IB)—The Goinage Metals 724
15.5 Group 12 (IIB)—The Zinc Subgroup 729
15.6 Group .3 (IIIA)—The Scandium Family and Rare Earths 732
15.7 The Actinide Metals 737
15.8 Transition Metals, Groups 4 - 7 (IVA-VIIA) 738
15.9 Groups 8, 9. and 10 (Group VIII) 747
15.10 Compounds Containing Metal-Metal Bonds 751
General References 757
Problems 757

CHAPTER 16
Chemistry of Some Nonmetals 760
16.1 General Periodic Trends for Nonmetals 760
16.2 Nitrogen and Phosphorus 761
16.3 Oxygen, Sulfur, and Selenium 773
16.4 The Halogens 789
16.5 The Noble Gases 807
General References 812
Problems 813

CHAPTER 17
Cluster and Cage Compounds 816
17.1 Introduction 816
17.2 The Bonding Problem in Boranes 819
17.3 Structures of the Boron Hydrides 823
17.4 Molecular Orbital Description of Bonding in Boron Hydrides 826
17.5 Heteroboranes 832
17.6 Chemistry of the Boranes 834
xviii Contents

17.7 Synthesis of Boron Hydrides 841

17.8 Carboranes 843
17.9 Some Chemistry of Group 13 847
17.10 Cluster Compounds 854
17.11 Electron-Precise Compounds and their Relation to Clusters 877
General References 879
Problems 880

CHAPTER 18
Bioinorganic Chemistry 888
18.1 Essential Elements 888
18.2 Oxygen Utilization 893
18.3 Supply and Storage of Iron 901
18.4 Oxidation—Reduction Processes 905
18.5 Metalloenzymes 910
18.6 Vitamin Bi 2 919
18.7 Nitrogenase 922
18.8 Photosynthesis 924
18.9 Roles of Na + , K + , Mg 2+ , Ca 2+ , and Ion Pumps 926
General References 927
Problems 928

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