Principles of Inorganic Chemistry

Brian W. Pfennig, PhD, has 25 years of experience teaching advanced general chemistry, inorganic chemistry, and organometallic photochemistry at colleges including Franklin and Marshall, Haverford, Vassar, and Ursinus.

Preface to the Second Edition xiii

Acknowledgments xv

Chapter 1 The Structure of Matter 1

1.1 Science as an Art Form 1

1.2 Atomism 5

1.3 The Anatomy of an Atom 8

1.4 The Periodic Table of the Elements 14

1.5 The Nucleus 17

1.6 Nuclear Reactions 20

1.7 Radioactive Decay and the Band of Stability 23

1.8 The Shell Model of the Nucleus 29

1.9 The Origin of the Elements 32

1.9.1 The Big Bang 32

1.9.2 Big Bang Nucleosynthesis 32

1.9.3 Stellar Nucleosynthesis 33

1.9.4 The s-Process and the r-Process 37

Exercises 39

Bibliography 41

Chapter 2 The Structure of the Atom 43

2.1 The Wave-Like Properties of Light 43

2.2 The Electromagnetic Spectrum 44

2.3 The Interference of Waves 45

2.4 The Line Spectrum of Hydrogen 48

2.5 Energy Levels in Atoms 51

2.6 The Bohr Model of the Atom 54

2.6.1 In-Depth: Derivation of the Bohr Model of the Atom 56

2.7 The Wave-Like Properties of Matter 60

2.8 Circular Standing Waves and the Quantization of Angular Momentum 62

2.9 The Classical Wave Equation 64

2.10 The Particle in a Box Model 65

2.10.1 In-Depth: The Quantum Mechanical Behavior of Nanoparticles 67

2.11 The Heisenberg Uncertainty Principle 68

2.12 The Schroedinger Equation 70

2.13 The Hydrogen Atom 74

2.13.1 The Radial Wave Functions 76

2.13.2 The Angular Wave Functions 79

2.14 The Spin Quantum Number 83

2.15 The Topological Atom 85

2.15.1 In-Depth: Atomic Units 87

Exercises 88

Bibliography 90

Chapter 3 The Periodicity of the Elements 91

3.1 Introduction 91

3.2 Hydrogenic Orbitals in Polyelectronic Atoms 92

3.2.1 In-Depth: The Helium Atom 94

3.3 The Quantum Structure of the Periodic Table 95

3.4 Electron Configurations 98

3.5 Shielding and Effective Nuclear Charges 102

3.6 Ionization Energy 104

3.7 Electron Affinity 109

3.8 Theoretical Radii 111

3.8.1 In-Depth: How the Radius Affects Other Properties 114

3.9 Polarizability 116

3.10 The Metal-Nonmetal Staircase 118

3.11 Global Hardness 120

3.12 Electronegativity 121

3.13 The Uniqueness Principle 124

3.14 Diagonal Properties 125

3.15 Relativistic Effects 126

3.16 The Inert-Pair Effect 128

Exercises 129

Bibliography 131

Chapter 4 An Introduction to Chemical Bonding 133

4.1 The Definition of a Chemical Bond 133

4.2 The Thermodynamic Driving Force for Bond Formation 134

4.3 Lewis Structures and Formal Charges 138

4.3.1 Rules for Drawing Lewis Structures 140

4.4 Covalent Bond Lengths and Bond Dissociation Energies 143

4.5 Resonance 144

4.6 Electronegativity and Polar Covalent Bonding 147

4.7 Types of Chemical Bonds-The Triangle of Bonding 148

4.8 Atoms in Molecules 153

Exercises 159

Bibliography 160

Chapter 5 Molecular Geometry 163

5.1 X-Ray Crystallography and the Determination of Molecular Geometry 163

5.2 Linnett'S Double Quartet Theory 165

5.3 Valence-Shell Electron Pair Repulsion Theory 170

5.3.1 Rules for Determining the Geometry of a Molecule Using VSEPD Theory 171

5.4 The Ligand Close-Packing Model 183

5.5 A Comparison of the VSEPR and LCP Models 187

Exercises 188

Bibliography 190

Chapter 6 Symmetry and Spectroscopy 191

6.1 Symmetry Elements and Symmetry Operations 191

6.1.1 Identity, E 193

6.1.2 Proper Rotation, Cn 193

6.1.3 Reflection, 195

6.1.4 Inversion, i 196

6.1.5 Improper Rotation, Sn 196

6.2 Symmetry Groups 199

6.3 Molecular Point Groups 203

6.3.1 In-Depth: Dipole Moments 208

6.4 Representations of Symmetry Operations 210

6.5 Character Tables 217

6.5.1 Irreducible Representations and Characters 217

6.5.2 Degenerate Representations 218

6.5.3 Rules Regarding Irreducible Representations 219

6.5.4 Conjugate Matrices and Classes 220

6.5.5 Mulliken Symbols 222

6.6 Direct Products 224

6.7 Reducible Representations and the Great Orthogonality Theorem 229

6.8 Molecular Spectroscopy and the Selection Rules 234

6.8.1 Infrared Spectroscopy 236

6.8.2 Raman Spectroscopy 240

6.8.3 A Summary of the Selection Rules for Vibrational Spectroscopy 241

6.8.4 In-Depth: Resonance Raman Spectroscopy 241

6.9 Determining the Symmetries of the Normal Modes of Vibration 243

6.10 Determining a Molecule's Likely Geometry from Its Spectroscopy 249

6.11 Generating Symmetry Coordinates Using the Projection Operator Method 252

Exercises 263

Bibliography 269

Chapter 7 Structure and Bonding in Molecules 271

7.1 Molecules as Unique Entities 271

7.2 Valence Bond Theory 272

7.2.1 Diatomic Molecules 272

7.2.2 In-Depth: A Mathematical Treatment of VBT 273

7.2.3 Polyatomic Atoms and Hybridization 275

7.2.4 Variable Hybridization 281

7.2.5 Bent's Rule 283

7.2.6 Hypervalent Molecules 286

7.2.7 Sigma and Pi Bonding 288

7.2.8 Transition Metal Compounds 289

7.2.9 Limitations of Valence Bond Theory 293

7.3 Molecular Orbital Theory 293

7.3.1 Homonuclear Diatomics 293

7.3.2 In-Depth: A Mathematical Treatment of MOT 294

7.3.3 Mixing 302

7.3.4 Heteronuclear Diatomics 307

7.3.5 The Covalent to Ionic Transition in MOT 310

7.3.6 Polyatomic Molecules: H3 and H3+ 312

7.3.7 Correlation Diagrams and the Prediction of Molecular Geometry 316

7.3.8 A Brief Introduction to the Jahn-Teller Effect 318

7.3.9 AHn Molecules and Walsh Diagrams 320

7.3.10 In-Depth: Pearson's Symmetry Rules for Predicting the Structures of AHn Molecules 332

7.3.11 Polyatomic Molecules Having Pi Orbitals 334

7.4 The Complementarity of VBT and MOT 363

Exercises 365

Bibliography 367

Chapter 8 Structure and Bonding in Solids 369

8.1 Crystal Structures 1

8.1.1 The 14 Bravais Lattices 373

8.1.2 Closest-Packed Structures 377

8.1.3 The 32 Crystallographic Point Groups and 230 Space Groups 381

8.1.4 The Determination of Crystal Structures 386

8.1.5 The Bragg Diffraction Law 386

8.1.6 Miller Planes and Indexing Powder Patterns 387

8.1.7 In-Depth: Quasicrystals 392

8.2 Metallic Bonding 393

8.2.1 The Free Electron Model of Metallic Bonding 395

8.2.2 Band Theory of Solids 399

8.2.3 Conductivity in Solids 407

8.2.4 In-Depth: the p-n Junction and n-p-n Bipolar Junction Transistor 418

8.3 Ionic Bonding 421

8.3.1 In-Depth: High-Temperature Superconductors 429

8.3.2 Lattice Enthalpies and the Born-Haber Cycle 430

8.3.3 Ionic Radii and Pauling's Rules 436

8.3.4 In-Depth: the Silicates 449

8.3.5 Defects in Crystals 450

8.4 Types Of Crystalline Solids 453

8.4.1 Intermediate Types of Bonding in Solids 457

Exercises 465

Bibliography 475

Chapter 9 Chemical Structure and Reactivity 477

9.1 Acid-Base Chemistry 478

9.1.1 Definitions of Acids and Bases 478

9.1.2 Measuring the Strengths of Acids and Bases 485

9.1.3 Factors Affecting the Strengths of Acids and Bases 489

9.1.4 Pearson's Hard-Soft Acid-Base Theory 495

9.1.5 The Relationship Between HSAB Theory and FMO Theory 497

9.2 Redox Chemistry 499

9.2.1 The Relationship Between Acid-Base and Redox Chemistry 499

9.2.2 Rationalizing Trends in Standard Reduction Potentials 500

9.2.3 Quantum Structure Property Relationships 505

9.2.4 The Drago-Wayland Parameters 507

9.3 A Generalized View of Chemical Reactivity 509

Exercises 515

Bibliography 519

Chapter 10 Coordination Chemistry 521

10.1 An Overview of Coordination Chemistry 522

10.1.1 The Historical Development of Coordination Chemistry 523

10.1.2 Types of Ligands and Proper Nomenclature 525

10.1.3 Stability Constants 527

10.1.4 Isomers 531

10.1.5 Common Coordination Geometries 534

10.1.6 In-Depth: Five-Coordinate Compounds 537

10.1.7 The Shapes of the d-Orbitals 540

10.2 Models of Bonding in Coordination Compounds 541

10.2.1 Crystal Field Theory 541

10.2.2 Ligand Field Theory 555

10.2.3 Quantitative Measures of LF Strength 562

10.3 Electronic Spectroscopy of Coordination Compounds 572

10.3.1 Term Symbols 572

10.3.2 Tanabe-Sugano Diagrams 578

10.3.3 Electronic Absorptions and the Selection Rules 582

10.3.4 Using Tanabe-Sugano Diagrams to Interpret or Predict Electronic Spectra 585

10.3.5 The Effect of Reduced Symmetry on Electronic Transitions 597

10.3.6 The Jahn-Teller Effect 598

10.3.7 Charge Transfer Transitions 599

10.3.8 Magnetic Properties of Coordination Compounds 600

10.3.9 Diamagnetism 603

10.3.10 Paramagnetism 603

10.3.11 Antiferromagnetism 604

10.3.12 Ferromagnetism 604

10.3.13 Ferrimagnetism 605

Exercises 605

Bibliography 610

Chapter 11 Reactions of Coordination Compounds 613

11.1 An Introduction to Kinetics and Reaction Coordinate Diagrams 613

11.1.1 Zero-Order Reactions 614

11.1.2 First-Order Reactions (Irreversible) 615

11.1.3 First-Order Reactions (Reversible and Coming to Equilibrium) 616

11.1.4 Simple Second-Order Reactions (Irreversible) 617

11.1.5 Complex Second-Order Reactions (Reversible and Coming to Equilibrium) 617

11.1.6 Complex Second-Order Reactions (Irreversible) 618

11.1.7 Pseudo First-Order Reactions 618

11.1.8 Consecutive First-Order Reactions and the Steady-State Approximation 619

11.1.9 Competing Mechanisms 619

11.1.10 Summary of the Common Rate Laws 620

11.1.11 The Arrhenius Equation 620

11.1.12 Activation Parameters 621

11.2 Octahedral Substitution Reactions 623

11.2.1 Associative (A) Mechanisms 624

11.2.2 Interchange (I) Mechanisms 624

11.2.3 Dissociative (D) Mechanisms 625

11.2.4 Acid and Base Catalysis 628

11.2.5 Ligand Field Activation Energies 629

11.3 Square Planar Substitution Reactions 631

11.3.1 The Trans Effect 635

11.3.2 The Effects of the Leaving Group and the Nucleophile 637

11.3.3 MOT and Square Planar Substitution 638

11.4 Electron Transfer Reactions 640

11.4.1 Outer-Sphere Electron Transfer 641

11.4.2 The Franck-Condon Principle 641

11.4.3 Marcus Theory 645

11.4.4 Inner-Sphere Electron Transfer 648

11.4.5 Mixed-Valence Compounds 652

Exercises 655

Bibliography 658

Chapter 12 Organometallic Chemistry 659

12.1 Introduction to Organometallic Chemistry 659

12.2 Electron Counting and the 18-Electron Rule 660

12.3 Carbonyl Ligands 663

12.4 Nitrosyl Ligands 668

12.5 Hydride and Dihydrogen Ligands 670

12.6 Phosphine Ligands 672

12.7 Ethylene and Related Ligands 674

12.8 Cyclopentadiene and Related Ligands 678

12.9 Carbenes, Carbynes, and Carbidos 682

Exercises 684

Bibliography 687

Chapter 13 Reactions of Organometallic Compounds 689

13.1 Some General Principles 689

13.2 Organometallic Reactions Involving Changes at the Metal 689

13.2.1 Ligand Substitution Reactions 689

13.2.2 Oxidative Addition and Reductive Elimination 692

13.3 Organometallic Reactions Involving Changes at the Ligand 705

13.3.1 Insertion and Elimination Reactions 705

13.3.2 Nucleophilic Attack on the Ligands 709

13.3.3 Electrophilic Attack on the Ligands 710

13.4 Metathesis Reactions 711

13.4.1 -Bond Metathesis 711

13.4.2 Ziegler-Natta Polymerization of Alkenes 712

13.4.3 -Bond Metathesis 713

13.5 A Summary of Organometallic Reaction Mechanisms 714

13.6 Organometallic Catalytic Cycles 714

13.6.1 Catalytic Hydrogenation 716

13.6.2 Hydroformylation 717

13.6.3 The Wacker-Smidt Process 719

13.6.4 The Monsanto Acetic Acid Process 720

13.6.5 Palladium-Catalyzed Cross-Coupling Mechanisms 721

13.7 The Isolobal Analogy and the Relationship to Main Group Chemistry 725

13.8 Closing Remarks 728

Exercises 729

Bibliography 732

Appendix: A Derivation of the Classical Wave Equation 733

Bibliography 734

Appendix: B Derivation of the Schroedinger Equation 735

Appendix: C Postulates of Quantum Mechanics 739

Bibliography 741

Appendix: D Atomic Term Symbols and Spin-Orbit Coupling 743

Extracting Term Symbols Using Russell-Saunders Coupling 744

Extracting Term Symbols Using jj Coupling 747

Correlation Between RS (LS) Coupling and jj Coupling 748

Appendix: E Character Tables 751

Bibliography 763

Appendix: F Direct Product Tables 765

Bibliography 769

Appendix: G Reducing Representations by the Process of Diagonalization 771

Appendix: H Correlation Tables 775

Bibliography 781

Appendix: I The Harmonic Oscillator Model 783

Bibliography 786

Appendix: J Molecular Term Symbols 787

Appendix: K The 230 Space Groups 791

Bibliography 795