MODERN INORGANIC
CHEMISTRY Second Edition
William L. Jolly Professor of Chemistry
University of California, Berkeley
McGraw-Hill, Inc. New York St. Louis San Francisco Auckland Bogota Caracas
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CONTENTS
Preface xiü
Chapter 1 Electron Configurations of Atoms and the Periodic Table 1 Quantum Numbers 1 Orbital Shapes and Energies for the Hydrogen Atom 3 Electron Configurations of Atoms and Ions 10 The Periodic Table 13 Ionization-Energy Trends 15 Atomic-Size Trends 21 Relativistic Effects 22 Oxidation States of the Lanthanides and Actinides 23 Problems 24
Chapter 2 Symmetry and the Elements of Group Theory 26 Symmetry Operations and Symmetry Elements 27 Point Groups 29 Character Tables and Irreducible Representations 32 Reducible Representations 38 Problems 40
Chapter 3 Covalent Bonding 42 The Lewis Octet Theory 42 The Isoelectronic Principle 48 Bond Distances 52 Bond Strength 57
Dissociation Energies / Bond Energies / Force Constants
VI CONTENTS
Bond Polarity Dipole Moments / Nuclear Magnetic Resonance / Nuclear Quadrupole Resonance / Mössbauer Spectroscopy / X-ray Photoelectron Spectroscopy / Electronegativities
Prediction of Molecular Topology Valence-Shell Electron Repulsion
Effective Coordination Number 2 / Effective Coordination Number 3 / Effective Coordination Number 4 / Effective Coordination Number 5 / Effective Coordination Number 6 / Effective Coordination Number 7 / A Caveat
Conformational Isomerism Based on Bond Rotations Problems
65
76 77
91 94
Chapter 4 Molecular Orbital Theory Simple LCAO Theory Criteria for Stable Molecular Orbitals Sigma, Pi, and Delta Molecular Orbitals Diatomic Molecules Electron Density Contour Maps Symmetry and Polyatomic Molecules Hybridization Walsh Diagrams Pi Bonding Beyond the First Row of the Periodic Table Simple Hückel Theory Hyperconjugation Calculations
Extended Hückel Theory / SCF Methods Problems
97
97 104 105 106 109 116 122 126 128 130 134 137
143
Chapter 5 Thermodynamic Aspects of Inorganic Chemistry Thermodynamic Functions Applications to Synthesis
Hydrazine / Fluorides from Oxides / Gas-Solid Equilibria Reduction Potentials
The Use of Tabulated Potentials / Dependence of Potentials on pH / Reduction-Potential Diagrams
Problems
145
145 146
151
163
Chapter 6 The Kinetics and Mechanisms of Reactions Rate Laws and Mechanisms The Steady State Catalysis Activated Complex Theory Reactions of Hydrogen with Halogens Orbital Symmetry Effects Explosions Stratospheric Ozone Reactions
164
164 166 167 168 170 175 177 181
CONTENTS vii
Mechanisms of Oxyanion Reactions 182 Differences Between 1- and 2-Equivalent Oxidizing Agents / The Landolt Clock Reaction
Problems 187
Chapter 7 Compounds of Hydrogen 189 Classification of the Hydrides 189
Saline Hydrides / Metallic Hydrides / Hydrogen Storage with Metallic Hydrides / Transition-Metal Hydride Complexes / Nonmetal Hydrides
Hydridic and Protonic Character 198 Problems 200
Chapter 8 Acid-Base Reactions 201 Gas-Phase Proton Affinities 201
Proton Affinities of Anions / Proton Affinities of Neutral Molecules
Aqueous Acidities of Protonic Acids 207 Binary Hydrides / Hydroxy Acids / Transition-Metal Carbonyl Hydrides
Hydrogen Bonding 214 Kinetics of Proton-Transfer Reactions 223 The Entropy of Ionization of Aqueous Acids 225 Some Special Aqueous Acids 226 Acids and Bases in Protonic Solvents 229 Acids and Bases in Aprotic Solvents 235 Lewis Acid-Base Theory 235 Problems 241
Chapter 9 Solvated Electrons 244 The Hydrated Electron 244 Metal-Ammonia Solutions 249
Physical Characteristics / The Miscibility Gap and Metal Ammoniates / Reactions / Kinetics
Alkali-Metal Anions and Electrides 256 Problems 258
Chapter 10 Boron Hydrides, Their Derivatives, and Main-Group Clusters 260 Syntheses 260
The Synthesis of Boron Hydrides / The Synthesis of Borane Anions / The Synthesis of Carboranes
Structure and Bonding 264 Three-Center Bonding / MO Theory of Clusters
Metallocarboranes and Metalloboranes 270 Other Main-Group Cluster Compounds 272
"Magic Numbers" Problems 276
VÜi CONTENTS
Chapter 11 The Solid State 278 Classification of Bonds and Crystals 278
Crystals Containing Finite Complexes / Crystals Containing Infinite One-Dimensional Complexes / Crystals Containing Infinite Two-Dimensional Complexes / Crystals Containing Infinite Three-Dimensional Complexes
The Effect of Radius Ratio and Charge on Structure 295 Lattice Energy 299 Application of the Isoelectronic Principle 303 Glasses 304 Polymers 305 Problems 307
Chapter 12 Metals and Metallic Compounds 309 Bonding Energies and Structures 309
Hume-Rothery Compounds 314 Band Theory 316
Electrical Conductivity / Ferromagnetism Metallic Compounds 325
"One-Dimensional" Metallic Compounds / "Two-Dimensional" Metallic Compounds
Superconductivity 335 Problems 339
Chapter 13 Semiconductors 341 Preparation of Semiconductors 343 Band Gaps 345 Defect Semiconductors 346 Controlled-Valence Semiconductors 347 Applications 348
The Photovoltaic Cell / The Photoelectrolytic Cell / The Rectifier / The Insulated-Gate Field-Effect Transistor
Amorphous Semiconductors 353 Problems 354
Chapter 14 Introduction to Transition-Metal Chemistry 356 Oxidation States 356 Colors 357 Magnetism 357 Complexes 358 Catalysis 358 Coordination Geometry 359
Coordination Number 2 / Coordination Number 3 / Coordination Number 4 / Coordination Number 5 / Coordination Number 6 / Coordination Number 7 / Coordination Number 8 / Higher Coordination Numbers / The Relative Prevalence of Coordination Numbers 4, 6, 8, and 12
CONTENTS IX
Ligands 367 Complexes of Monodentate Ligands / Polydentate Ligands / Pi Complexes
Isomerism 382 Cis-Trans Isomerism / Optical Isomerism / Linkage Isomerism
Structural Reorganization 388 Problems 388
Chapter 15 The Bonding in Coordination Compounds 390 Electrostatic Ligand-Field Theory 391 Molecular Orbital Theory 394
Pi Bonding / The Metal-Metal Bond Weak- and Strong-Field Complexes 402 Problems 403
Chapter 16 The 18-Electron Rule 404 Oxidation-State Ambiguity 411
Nitrosyls / Bipyridyl Complexes / Metal Dithienes Polyhedral Transition-Metal Cluster Compounds 416
Some Difficult Cases / Applications / High-Nuclearity Clusters
Problems 431
Chapter 17 Electronic Spectra of Coordination Compounds 435 Ligand-Field Spectra 437
The Ligand-Field Splitting, A, and the Interelectronic Repulsion Parameter, B I Spectral Calculations
Charge-Transfer Spectra 449 Ligand-to-Metal Charge Transfer / Metal-to-Ligand Charge Transfer
Spectra of Compounds with Metal-Metal Bonds 451 Photoelectron Spectra 452 Problems 453
Chapter 18 Other Properties of Coordination Compounds 454 Paramagnetism 454
Magnetic Moment / High-Spin-Low-Spin Crossover / Orbital Angular Momentum
Ferromagnetism, Ferrimagnetism, and Antiferromagnetism 462 Jahn-Teller Distortions 465 Ligand-Field Stabilization Energy 468 Structural Effects of Ligand-Metal Pi Bonding 472
TT-Donor Bonding / T7-Acceptor Bonding Other Effects of Back Bonding 477 Problems 480
X CONTENTS
Chapter 19 Kinetics and Mechanisms of Reactions of Transition-Metal Complexes 482 Substitution Reactions of Octahedral Complexes 482
Lability / Mechanisms Substitution Reactions of Square Planar Complexes 489
The Kinetic Trans Effect / Effect of Entering and Leaving Ligands
Oxidation-Reduction Reactions 494 Outer-Sphere Electron Transfer / Inner-Sphere Redox Reactions / Electron Transfer Through Extended Bridges / Mixed-Valence Compounds / Unstable Intermediate Oxidation States
Problems 504
Chapter 20 Homogeneous Catalysis of Organic Reactions 506 Olefin Hydrogenation 510 Olefin Dimerization and Metathesis 511 Olefin Isomerization 514 Hydroformy lation 515 Water Gas Shift Reaction 516 Acetic Acid from Ethylene 516 Template Syntheses 518 Problems 519
Chapter 21 Heterogeneous Catalysis 521 Effects of Surface Site on Adsorption 521 Effects of Surface Coverage on Adsorption of Carbon Monoxide 527 The Fischer-Tropsch Process 530 Ziegler-Natta Olefin Polymerization 533 Ammonia Synthesis 534 The Photographic Process 536 Electrode Surface Modification 540 Catalysis by Metal Clusters 542 Problems 545
Chapter 22 Some Biological Systems 546 Metalloporphyrins and Related Systems 546
Hemoglobin and Myoglobin / Vitamin B l2
Iron-Containing Proteins 558 Iron-Sulfur Proteins / Nitrogen Fixation / Ferritin
CH-Dichlorodiammineplatinum(II) Anticancer Activity 566 Carbonic Anhydrase 567 Superoxide Dismutases 568 Problems 570
Appendixes A Units and Conversion Factors 571 B Term Symbols for Free Atoms and Ions 574
CONTENTS Xi
C Electron Affinities 577 Electron Affinities of Atoms / Electron Affinities of Molecules and Radicals
D Ionization Energies 580 E Selected Values of Thermodynamic Data 581 F Ionic Radii 592 G Inorganic Nomenclature 598
Formulas and Names of Compounds in General 598 Names for Ions and Radicals 599 Acids 601 Salts Containing Acid Hydrogen 602 Coordination Compounds 602
Alternative Modes of Linkage of Some Ligands / Use of Abbreviations / Complexes with Unsaturated Molecules or Groups / Compounds with Bridging Atoms or Groups / Homoatomic Aggregates
Prefixes or Affixes Used in Inorganic Nomenclature 606 Multiplying Affixes / Structural Affixes / Substitutional Affixes
Answers to Selected Problems 608 Indexes
Formula Index 623 Subject Index 635
