Brian W. Pfennig, PhD, received his undergraduate B.S. degree in chemistry at Albright College in 1988. He earned his Ph.D. in 1992 in the field of physical inorganic chemistry at Princeton University with Dr. Andrew B. Bocarsly, studying the photochemistry of organometallic sandwich compounds and electron transfer in multinuclear mixed-valence coordination compounds. Dr. Pfennig has held a number of different teaching appointments at small liberal arts colleges, including Franklin & Marshall College, Haverford College, Vassar College, and Ursinus College. During his 20-year teaching career, he has taught general chemistry, an accelerated one-semester general chemistry course, both introductory and advanced inorganic chemistry, bio-inorganic chemistry, and inorganic and organometallic photochemistry, as well as serving as the general chemistry laboratory coordinator at Ursinus College for the past 10 years. He is also actively engaged in research with undergraduates in the areas of inorganic photochemistry, electrochemistry, and electron transfer processes occurring in multinuclear mixed-valence coordination compounds. He has also published several papers in the area of chemical education.

Preface xi

Acknowledgements xv

Chapter 1 The Composition of Matter 1

1.1 Early Descriptions of Matter 1

1.2 Visualizing Atoms 6

1.3 The Periodic Table 8

1.4 The Standard Model 9

Exercises 12

Bibliography 13

Chapter 2 The Structure of the Nucleus 15

2.1 The Nucleus 15

2.2 Nuclear Binding Energies 16

2.3 Nuclear Reactions: Fusion and Fission 17

2.4 Radioactive Decay and The Band of Stability 22

2.5 The Shell Model of the Nucleus 27

2.6 The Origin of the Elements 30

Exercises 38

Bibliography 39

Chapter 3 A Brief Review of Quantum Theory 41

3.1 TheWavelike Properties of Light 41

3.2 Problems with the Classical Model of the Atom 48

3.3 The Bohr Model of The Atom 55

3.4 Implications of Wave-Particle Duality 58

3.5 Postulates of Quantum Mechanics 64

3.6 The Schrödinger Equation 67

3.7 The Particle in a Box Problem 70

3.8 The Harmonic Oscillator Problem 75

Exercises 78

Bibliography 79

Chapter 4 Atomic Structure 81

4.1 The Hydrogen Atom 81

4.1.1 The Radial Wave Functions 82

4.1.2 The Angular Wave Functions 86

4.2 Polyelectronic Atoms 91

4.3 Electron Spin and the Pauli Principle 93

4.4 Electron Configurations and the Periodic Table 96

4.5 Atomic Term Symbols 98

4.5.1 Extracting Term Symbols Using Russell–Saunders Coupling 100

4.5.2 Extracting Term Symbols Using jj Coupling 102

4.5.3 Correlation between RS (LS) Coupling and jj Coupling 104

4.6 Shielding and Effective Nuclear Charge 105

Exercises 107

Bibliography 108

Chapter 5 Periodic Properties of the Elements 109

5.1 The Modern Periodic Table 109

5.2 Radius 111

5.3 Ionization Energy 118

5.4 Electron Affinity 121

5.5 The Uniqueness Principle 122

5.6 Diagonal Properties 124

5.7 The Metal–Nonmetal Line 125

5.8 Standard Reduction Potentials 126

5.9 The Inert-Pair Effect 129

5.10 Relativistic Effects 130

5.11 Electronegativity 133

Exercises 136

Bibliography 137

Chapter 6 An Introduction to Chemical Bonding 139

6.1 The Bonding in Molecular Hydrogen 139

6.2 Lewis Structures 140

6.3 Covalent Bond Lengths and Bond Dissociation Energies 144

6.4 Resonance 146

6.5 Polar Covalent Bonding 149

Exercises 153

Bibliography 154

Chapter 7 Molecular Geometry 155

7.1 The VSEPR Model 155

7.2 The Ligand Close-Packing Model 170

7.3 A Comparison of The VSEPR and LCP Models 175

Exercises 176

Bibliography 177

Chapter 8 Molecular Symmetry 179

8.1 Symmetry Elements and Symmetry Operations 179

8.1.1 Identity, E 180

8.1.2 Proper Rotation, Cn 181

8.1.3 Reflection, σ 182

8.1.4 Inversion, i 183

8.1.5 Improper Rotation, Sn 183

8.2 Symmetry Groups 186

8.3 Molecular Point Groups 191

8.4 Representations 195

8.5 Character Tables 202

8.6 Direct Products 209

8.7 Reducible Representations 214

Exercises 222

Bibliography 224

Chapter 9 Vibrational Spectroscopy 227

9.1 Overview of Vibrational Spectroscopy 227

9.2 Selection Rules for IR and Raman-Active Vibrational Modes 231

9.3 Determining The Symmetries of The Normal Modes of Vibration 235

9.4 Generating Symmetry Coordinates Using The Projection Operator Method 243

9.5 Resonance Raman Spectroscopy 252

Exercises 256

Bibliography 258

Chapter 10 Covalent Bonding 259

10.1 Valence Bond Theory 259

10.2 Molecular Orbital Theory: Diatomics 278

10.3 Molecular Orbital Theory: Polyatomics 292

10.4 Molecular Orbital Theory: pi Orbitals 305

10.5 Molecular Orbital Theory: More Complex Examples 317

10.6 Borane and Carborane Cluster Compounds 325

Exercises 334

Bibliography 336

Chapter 11 Metallic Bonding 339

11.1 Crystalline Lattices 339

11.2 X-Ray Diffraction 345

11.3 Closest-Packed Structures 350

11.4 The Free Electron Model of Metallic Bonding 355

11.5 Band Theory of Solids 360

11.6 Conductivity in Solids 374

11.7 Connections Between Solids and Discrete Molecules 383

Exercises 384

Bibliography 388

Chapter 12 Ionic Bonding 391

12.1 Common Types of Ionic Solids 391

12.2 Lattice Enthalpies and The Born–Haber Cycle 398

12.3 Ionic Radii and Pauling’s Rules 404

12.4 The Silicates 417

12.5 Zeolites 422

12.6 Defects in Crystals 423

Exercises 426

Bibliography 428

Chapter 13 Structure and Bonding 431

13.1 A Reexamination of Crystalline Solids 431

13.2 Intermediate Types of Bonding in Solids 434

13.3 Quantum Theory of Atoms in Molecules (QTAIM) 443

Exercises 449

Bibliography 452

Chapter 14 Structure and Reactivity 453

14.1 An Overview of Chemical Reactivity 453

14.2 Acid–Base Reactions 455

14.3 Frontier Molecular Orbital Theory 467

14.4 Oxidation–Reduction Reactions 473

14.5 A Generalized View of Molecular Reactivity 475

Exercises 480

Bibliography 481

Chapter 15 An Introduction to Coordination Compounds 483

15.1 A Historical Overview of Coordination Chemistry 483

15.2 Types of Ligands and Nomenclature 487

15.3 Stability Constants 490

15.4 Coordination Numbers and Geometries 492

15.5 Isomerism 498

15.6 The Magnetic Properties of Coordination Compounds 501

Exercises 506

Bibliography 508

Chapter 16 Structure, Bonding, and Spectroscopy of Coordination Compounds 509

16.1 Valence Bond Model 509

16.2 Crystal Field Theory 512

16.3 Ligand Field Theory 525

16.4 The Angular Overlap Method 534

16.5 Molecular Term Symbols 541

16.5.1 Scenario 1—All the Orbitals Are Completely Occupied 546

16.5.2 Scenario 2—There Is a Single Unpaired Electron in One of the Orbitals 546

16.5.3 Scenario 3—There Are Two Unpaired Electrons in Two Different Orbitals 546

16.5.4 Scenario 4—A Degenerate Orbital Is Lacking a Single Electron 547

16.5.5 Scenario 5—There Are Two Electrons in a Degenerate Orbital 547

16.5.6 Scenario 6—There Are Three Electrons in a Triply Degenerate Orbital 547

16.6 Tanabe–Sugano Diagrams 549

16.7 Electronic Spectroscopy of Coordination Compounds 554

16.8 The Jahn–Teller Effect 564

Exercises 566

Bibliography 570

Chapter 17 Reactions of Coordination Compounds 573

17.1 Kinetics Overview 573

17.2 Octahedral Substitution Reactions 577

17.2.1 Associative (A) Mechanism 578

17.2.2 Interchange (I) Mechanism 579

17.2.3 Dissociative (D) Mechanism 580

17.3 Square Planar Substitution Reactions 585

17.4 Electron Transfer Reactions 593

17.5 Inorganic Photochemistry 606

17.5.1 Photochemistry of Chromium(III) Ammine Compounds 607

17.5.2 Light-Induced Excited State Spin Trapping in Iron(II) Compounds 611

17.5.3 MLCT Photochemistry in Pentaammineruthenium(II) Compounds 615

17.5.4 Photochemistry and Photophysics of Ruthenium(II) Polypyridyl Compounds 617

Exercises 622

Bibliography 624

Chapter 18 Structure and Bonding in Organometallic Compounds 627

18.1 Introduction to Organometallic Chemistry 627

18.2 Electron Counting and the 18-Electron Rule 628

18.3 Carbonyl Ligands 631

18.4 Nitrosyl Ligands 635

18.5 Hydride and Dihydrogen Ligands 638

18.6 Phosphine Ligands 640

18.7 Ethylene and Related Ligands 641

18.8 Cyclopentadiene and Related Ligands 645

18.9 Carbenes, Carbynes, and Carbidos 648

Exercises 651

Bibliography 654

Chapter 19 Reactions of Organometallic Compounds 655

19.1 Some General Principles 655

19.2 Organometallic Reactions Involving Changes at the Metal 656

19.2.1 Ligand Substitution Reactions 656

19.2.2 Oxidative Addition and Reductive Elimination 658

19.3 Organometallic Reactions Involving Changes at the Ligand 664

19.3.1 Insertion and Elimination Reactions 664

19.3.2 Nucleophilic Attack on the Ligands 667

19.3.3 Electrophilic Attack on the Ligands 669

19.4 Metathesis Reactions 670

19.4.1 π-Bond Metathesis 670

19.4.2 Ziegler–Natta Polymerization of Alkenes 671

19.4.3 σ-Bond Metathesis 671

19.5 Commercial Catalytic Processes 674

19.5.1 Catalytic Hydrogenation 674

19.5.2 Hydroformylation 674

19.5.3 Wacker–Smidt Process 676

19.5.4 Monsanto Acetic Acid Process 677

19.6 Organometallic Photochemistry 678

19.6.1 Photosubstitution of CO 678

19.6.2 Photoinduced Cleavage of Metal–Metal Bonds 680

19.6.3 Photochemistry of Metallocenes 682

19.7 The Isolobal Analogy and Metal–Metal Bonding in Organometallic Clusters 683

Exercises 689

Bibliography 691

Appendix: A Derivation of the Classical Wave Equation 693

Bibliography 694

Appendix: B Character Tables 695

Bibliography 708

Appendix: C Direct Product Tables 709

Bibliography 713

Appendix: D Correlation Tables 715

Bibliography 721

Appendix: E The 230 Space Groups 723

Bibliography 728

Index 729

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