Ebook
Principles of Inorganic ChemistryISBN: 9781118859018
760 pages
March 2015

Description
 Takes a principlesbased, group and molecular orbital theory approach to inorganic chemistry
 The first inorganic chemistry textbook to provide a thorough treatment of group theory, a topic usually relegated to only one or two chapters of texts, giving it only a cursory overview
 Covers atomic and molecular term symbols, symmetry coordinates in vibrational spectroscopy using the projection operator method, polyatomic MO theory, band theory, and TanabeSugano diagrams
 Includes a heavy dose of group theory in the primary inorganic textbook, most of the pedagogical benefits of integration and reinforcement of this material in the treatment of other topics, such as frontier MO acidbase theory, band theory of solids, inorganic photochemistry, the JahnTeller effect, and Wade's rules are fully realized
 Very physical in nature compare to other textbooks in the field, taking the time to go through mathematical derivations and to compare and contrast different theories of bonding in order to allow for a more rigorous treatment of their application to molecular structure, bonding, and spectroscopy
 Informal and engaging writing style; worked examples throughout the text; unanswered problems in every chapter; contains a generous use of informative, colorful illustrations
Table of Contents
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 WaveParticle 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 InertPair 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 ClosePacking 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 RamanActive 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 XRay Diffraction 345
11.3 ClosestPacked 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 LightInduced 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 18Electron 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 πBond Metathesis 670
19.4.2 Ziegler–Natta Polymerization of Alkenes 671
19.4.3 σBond 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
Author Information
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 mixedvalence 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 20year teaching career, he has taught general chemistry, an accelerated onesemester general chemistry course, both introductory and advanced inorganic chemistry, bioinorganic 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 mixedvalence coordination compounds. He has also published several papers in the area of chemical education.