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Inorganic Chemistry - GBV

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Inorganic Chemistry PRINCIPLES AND APPLICATIONS lan S. Butler John F. Harrod McGill University The Benjamin/Cummings Publishing Company, Inc. Redwood City, California • Fort Collins, Colorado Menlo Park, California • Reading, Massachusetts • New York Don Mills, Ontario • Wokingham, U.K. • Amsterdam • Bonn Sydney • Singapore • Tokyo • Madrid • San Juan
Transcript

Inorganic Chemistry PRINCIPLES AND APPLICATIONS

lan S. Butler John F. Harrod McGill University

The Benjamin/Cummings Publishing Company, Inc. Redwood City, California • Fort Collins, Colorado Menlo Park, California • Reading, Massachusetts • New York Don Mills, Ontario • Wokingham, U.K. • Amsterdam • Bonn Sydney • Singapore • Tokyo • Madrid • San Juan

Contents

1 What Is Inorganic Chemistry? 1 Bibliography 11

Part One Theoretical Basis 13

2 Review of Atomic Theory and Atomic Properties 15 2.1 A Historical Perspective 15 2.2 The Quantum Mechanical View of the Atom 19 2.3 Many-Electron Atoms and the Periodic Table 33 2.4 Some Important Trends in Atomic Properties 45 Bibliography 60 Problems 63

3 Theories of the Chemical Bond 68 3.1 Empirical Theories 68 3.2 Wave Mechanical Theories 73 Bibliography 104 Problems 105

4 The lonic Bond 108 4.1 Formation of Ions and Lattices 108 4.2 Relationship Between lonic and Covalent Bonding 112

x

CONTENTS Xi

4.3 Close Packing of Spheres 115 4.4 Some Common Ionic Structures Based on

Close Packing 118 4.5 Some Simple Structures Not Based on Close Packing 121 4.6 Some Ternary Oxide Structures 124 4.7 Factors Influencing Structure 125 4.8 Friction, Lubrication, and Wear 128 Bibliography 131 Problems 131

Part Two Molecular Structure and Analytical Methods 135

5 Molecular Symmetry in Inorganic Chemistry 137 5.1 Molecular Symmetry and Group Theory 138 5.2 Orbital Symmetry 154 Bibliography 159 Problems 159

6 Infrared and Raman Spectroscopy 162 6.1 Theory of Infrared and Raman Spectroscopy 163 6.2 Applying Group Theory to Molecular Vibrations 180 6.3 Some Applications of Infrared and Raman Spectroscopy in

Inorganic Chemistry 189 Bibliography 194 Problems 195

7 Resonance Spectroscopies 198 7.1 Nuclear Magnetic Resonance Spectroscopy 198 7.2 Nuclear Quadrupole Resonance Spectroscopy 213 7.3 Mössbauer Spectroscopy 216 7.4 Electron-Spin Resonance Spectroscopy 221 Bibliography 225 Problems 226

8 Photoelectron, X-Ray Absorption, and Mass Spectroscopies and X-Ray Crystallography 229 8.1 Photoelectron Spectroscopy 230 8.2 Extended X-Ray Absorption Fine Structure and X-Ray

Absorption Near-Edge Structure Spectroscopies 237 8.3 Mass Spectroscopy 241 8.4 X-Ray Crystallography 246 8.5 Concluding Remarks 253 Bibliography 253 Problems 255

Part Three Periodic Trends for the Elements and Simple Compounds 259

9 Hydrogen and Its Compounds 261 9.1 Hydrogen 261 9.2 Types of Binary Hydrogen Compounds 265 9.3 Hydrides of Croups IA and IIA (1 and 2) 267 9.4 Hydrides and Complex Hydrides of Group 1IIA (13) 268 9.5 Hydrides of Group IVA (14) 273 9.6 Hydrides of Croups VA and VIA (15 and 16) 277 9.7 Hydrogen Halides 285 9.8 Hydrides of the d- and f- Block Elements 287 Bibliography 290 Problems 291

10 Halides and Oxides of the Main Groups 292 10.1 Differences Between Hydrides, Oxides, and Halides 292 10.2 Groups IA and IIA (1 and 2) 297 10.3 Groups HIA and IVA (13 and 14) 301 10.4 Group VA (15) 317 10.5 Oxides and Halides of Group VIA (16) 327 10.6 Interhalogen and Noble Gas Compounds 331 Bibliography 335 Problems 335

11 Halides and Oxides of Transition Elements 338 11.1 Some General Considerations 338 11.2 Oxides of Transition Elements 340 11.3 Transition Metal Halides 345 11.4 Oxides and Halides of Group HIB (3):

Eanthanides and Actinides 354 Bibliography 356 Problems 357

Part Four Complex Compounds: Coordination Chemistry 359

12 Werner's Classical Coordination Theory 361 12.1 Historical Development of Coordination Chemistry 361 12.2 Types of Ligands 364 12.3 The Chelate Effect and Chelating Ligands 366 12.4 Naming Coordination Compounds 368 12.5 Geometries of Coordination Compounds 374

CONTENTS xiii

72.6 Isomerism in Coordination Compounds 382 Bibliography 387 Problems 387

13 Crystal Field Theory 390 13.1 Bonding in Coordination Compounds 390 13.2 Crystal Field Theory 391 13.3 Gemstones, Lasers, and Such 409 13.4 Some Structural and Thermodynamic Effects of

Crystal Fields 413 13.5 Some Kinetic Consequences of Crystal Field

Stabilization Energy 421 13.6 Breakdown of the Crystal Field Theory 422 Bibliography 425 Problems 426

14 Magnetic Properties of d- and {-Block Compounds 428 14.1 Theoretical Basis of Magnetochemistry 428 14.2 Magnetic Properties of 3d Compounds 431 14.3 Magnetic Behavior of Lanthanide Compounds 433 14.4 Cooperative Interactions 433 Bibliography 438 Problems 439

Part Five Complex Compounds: Rings, Chains, Cages, and Clusters 441

15 Inorganic Polymers 443 15.1 The Bridge Between Small and Infinite Molecules 443 15.2 Polyboranes 448 15.3 Polysilylenes 459 Bibliography 462 Problems 462

10 Heteropolar Inorganic Polymers 464 16.1 Ring and Chain Molecules Containing Nitrogen 465 16.2 Oxyanions and Polyoxyanions 471 16.3 Organopolysiloxanes: The Silicones 483 16.4 Some Transition Metal Polyoxyanions 486 Bibliography 491 Problems 492

17 Metal Cluster Compounds 494 Bibliography 502 Problems 503

xiv CONTENTS

Part Six Solid-State Chemistry 505

18 Ordered Solids 507 18.1 Bonding in Solids 509 18.2 Storage Batteries: Old and New 529 18.3 A Brief Note on Corrosion and Tarnishing 532 Bibliography 535 Problems 535

19 Amorphous Solids 538 19.1 General Considerations and Definitions 538 19.2 Glassy Metals 540 19.3 Chalogenide Glasses 541 19.4 Oxide Glasses 546 19.5 Amorphous Carbon 549 Bibliography 550 Problems 550

Part Seven Solution Chemistry 553

20 Aqueous and Nonaqueous Solutions 555 20.1 Aqueous Solutions 555 20.2 Inorganic Chemistry in Nonaqueous Solvents 572 20.3 Electrochemistry 580 20.4 Inorganic Chemistry and the Environment 593 Bibliography 599 Problems 600

21 Mechanisms of Inorganic Reactions in Solution 602 21.1 Main Reaction Types 603 21.2 Substitution Reactions 605 21.3 Oxidation-Reduction Reactions 623 21.4 Fluxional Molecules 627 21.5 Oxidative-Addition/Reductive-Elimination Reactions 629 21.6 Free-Radical Reactions 631 21.7 Insertion Reactions 634 Bibliography 636 Problems 637

Part Eight Advanced Topics in Coordination Chemistry 639

22 Organometallic Chemistry 641 22.1 The Metal-Carbon Bond 643 22.2 Main-Group Organometallics 647

CONTENTS XV

22.3 Sigma-Bonded Transition Metal Complexes 652 22.4 Transition Metal Carbonyls 656 22.5 Transition Metal Thiocarbonyl and Selenocarbonyl

Complexes 670 22.6 Nitric Oxide Complexes 674 22.7 Tertiary Phosphine Complexes 676 22.8 Transition Metal Complexes of Unsaturated

Organic Ligands 679 22.9 Organometallics of i-Block Elements 692 22.10 Concluding Remarks 694 Bibliography 696 Problems 697

23 Catalysis by Coordination and Organometallic Complexes 700 23.1 Ziegler-Natta Alkene Polymerization 701 23.2 Activation of Hydro gen, Oxygen, and Other

Small Molecules 703 Bibliography 718 Problems 719

24 Bioinorganic Chemistry 721 24.1 What Is Bioinorganic Chemistry? 721 24.2 Sequestering and Storing Essential Elements 725 24.3 Herne Proteins and Managing Oxygen 729 24.4 Nonheme Proteins 744 24.5 Copper Proteins 748 24.6 Coenzyme B12 750 24.7 Nitrogen Fixation 753 Bibliography 757 Problems 757

Appendix I Some Important Character Tables 760

Appendix II Some Common Units and Conversion Factors 766

Appendix III Atomic Masses of Elements 769

Index 773


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