MODERN INORGANIC CHEMISTRY
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1 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 Hamburg Lisbon London Madrid Mexico Milan Montreal New Delhi Paris San Juan Säo Paulo Singapore Sydney Tokyo Toronto
2 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
3 VI CONTENTS Chapter 4 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 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 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 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
4 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
5 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
6 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 Chapter 18 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 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
7 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
8 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
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