Download Concepts and Models of Inorganic Chemistry

Concepts and Models
of Inorganic
Chemistry
Third Edition
Bodie E. Douglas
Universily of Pittsburgh
Darl H. McDaniel
University of Cincinnati
John J. Alexander
University of Cincinnati
John Wiley & Sons, Inc.
New York
Chichester
Brisbane
Toronto
Singapore
Contents
PART I
Some Basic Concepts
\
CHAPTER 1
Atomic Structure and the Periodic Table
3
1.1 Models in Chemistry
1.2 Historical Background
3
5
1.3 Atomic Structure and the Basis of the Periodic Table
1.4 Spectroscopic Terms and the Zeeman Effect; One-Electron Atoms
8
32
1.5
1.6
1.7
1.8
34
42
46
47
50
51
The Vector Model and Term Structure for Polyelectron Atoms
Ionization Energies
Electron Afflnities
Absolute Electronegativity and Absolute Hardness
General References
Problems
CHAPTER 2
Molecular Models
54
2.1 Review of Covalent Bonding
2.2 Valence Bond (Pauling-Slater) Theory
54
66
xi
xii
Contents
2.3 Shapes of Molecules
2.4 Electronegativity
2.5 Radii of Atoms in Covalent Compounds
2.6 The Hydrogen Bond
2.7 Weak Interactions in Covalent Substances
General References
Problems
72
82
88
92
99
102
102
CHAPTER 3
Symmetry
105
3.1
3.2
3.3
3.4
3.5
Introduction
Symmetry Elements and Symmetry Operations
Introduction to Groups
Symmetry Point Groups
Class Structure, Representations, and Character Tables
105
106
114
116
127
3.6 Chemical Applications of Symmetry
3.7 Summary of Terminology and Notation from Symmetry and
Group Theory
General References
Appendix 3.1 Matrix Representation of Transformation a n d
Matrix Multiplication
Appendix 3.2 The Direct Product of Representations
Problems
138
l4l
144
144
147
147
PART II
Bonding and Structure
149
CHAPTER 4
Discrete Molecules: Molecular Orbitals
151
4.1 Diatomic Molecules
151
4.2 Linnett's Double Quartet
4.3 Triatomic Molecules
4.4 Xenon Difluoride
163
166
176
4.5
4.6
4.7
4.8
177
185
188
193
196
196
Boron Trifluoride—A Group Theoretical Treatment
Diborane
Cyclic-Planar IT Molecules
Basis Sets and Frontier Orbitals
General References
Problems
Contents
CHAPTER 5
Inorganic Solids: lonic Models
xiii
198
5.1 Simple lonic Solids
199
5.2
5.3
5.4
5.5
5.6
204
206
211
212
220
Close Packing
lonic Struetures Based lipon Close-Packed Arrangements
Radius Katios f'or Stable Arrangements in lonic Crystals
Common Struetures of lonic Crystals
Notation for Struetures Based Upon Close Packing
5.7 lonic Kadii
5.8
5.9
5.10
5.11
5.12
Lattice Energy
Solubilities of lonic Substances
Giant Molecules
Struetures of Silicates
Crystal Struetures of Metals
General References
Problems
221
224
235
238
239
246
248
249
CHAPTER 6
Solid-State Chemistry
251
6.1 Crystal Structure
6.2 Defect Struetures
251
264
6.3
6.4
6.5
6.6
6.7
268
284
292
294
295
Electronic Structure of Solids
Graphite as a Two-Uimensional Solid
Metals. Insulators, and Semiconductors
Some Liniitations and Lxtensions of the Simple Band Theory
Superconductivity
6.8 Buckminsterfullerene
General References
Problems
300
303
304
PART III
Chemical Reactions
307
CHAPTER 7
Acids and Bases
309
7.1 Models of Acids and Bases
7.2 Protonic Acids
7.3 Acid—Base Behavior of the Binary Oxides and Aqua Cations
309
313
326
xiv
Contents
7.4 Nonprotonic Concepts of Acid-Base Reactions
7.5 The Drago-Wayland Equation
7.6 Solid Acids
General References
Problems
333
343
346
347
347
CHAPTER 8
Oxidation—Reduction Reactions
350
8.1 Conventions Covering Standard States
8.2 Methods of Determining Changes in Free Energy
350
352
8.3 Schematic Representation of Galvanic Cells
353
8.4
8.5
8.6
8.7
8.8
354
356
363
366
368
Conventions Regarding Cells
Calculations Using emf Data
Pourbaix (or Predominance Area) Diagrams
Geochemistry of Manganese
Periodic Trends among the Transition Elements
8.9 Some Redox Reactions of Nonmetals
8.10 Equilibrium Constants from emf Data
General References
Problems
370
372
373
373
PART IV
Coordination Chemistry
377
CHAPTER 9
Models and Stereochemistry
379
9.1 Introduction
9.2 Analytical Applications
9.3 Brief Summarv of Nomenclature of Coordination Compounds
379
381
383
9.4 Stabilities of Coordination Compounds
9.5 Werner's Coordination Theory
384
390
9.6 Valence Bond Models
9.7 Simple Electrostatic Models of Bonding
9.8 The Ligand-Field Theory
392
398
401
Contents
9.9
9.10
9.11
9.12
9.13
9.14
XV
Isomerism of Coordination Compounds
Coordination Number Four
Coordination Number Six
Coordination Number Five
Lower Coordination Numbers
Higher Coordination Numbers
411
413
415
424
427
428
9.15 Stereochemically Nonrigid and Fluxional Molecules
General References
Problems
432
437
438
CHAPTER 10
Spectra and Bonding
441
10.1 Introduction
441
10.2
10.3
10.4
10.5
Ligand-Field Spectra of Octahedral Complexes
Complexes of Lower Symmetry
Charge Transfer Bands
Circular üichroism and Optica! Rotatory Dispersion
442
459
463
465
10.6
10.7
10.8
10.9
Pictorial Molecular-Orbital Description of Bonding
Effects of TT Bonding
Group Theoretical Treatment
Comparison of the Oifferent Approaches to Bonding in
Coordination Compounds
General References
Problems
468
471
472
478
478
479
CHAPTER 11
Reaction Mechanisms
482
11.1
11.2
11.3
11.4
11.5
482
486
487
517
519
The Kinetic Model
Introduction to Ligand Substitution Reactions
Octahedral Complexes: Ligand Substitution Reactions
Racemization Reactions
Square-Planar Complexes: Ligand Substitution Reactions
11.6 Catalysis of Substitution by Redox Processes
11.7 Redox Reactions
528
528
11.8 Photochemical Reactions
General References
Problems
543
549
549
)
Contents
PART V
Organometallic
Chemistry
559
CHAPTER 12
General Principles
561
12.1 Introduction
12.2 Carbonyl Complexes
12.3 Bonding of Organic Ligands to Metals
562
562
577
12.4 Experimental Eviderice t'or Back-Üonation
12.5 Structural Characterization of Organometallic Compounds
597
603
12.6 The Isolobal Analogy
12.7 Dihydrogen Complexes
General References
Problems
605
606
609
609
CHAPTER 13
Survey of Organometallic Compounds
614
13.1 Some Chemistry of Olefin Complexes
614
13.2 Alkyne Complexes
615
13.3 Allyl Complexes
13.4 Butadiene Complexes
619
622
13.5 Cyclic TT Complexes
13.6 Compounds with Metal—Carbon a Bonds
13.7 Compounds with Multiple Metal-Carbon Bonds
General References
Problems
626
635
646
650
650
CHAPTER 14
Organometallic Reactions, Mechanisms, and Catalysis
653
14.1 Fundamental Reactions
14.2 Homogeneous Catalysis by Soluble Transition Metal Complexes
General References
Problems
653
685
697
697
xvii
Contents
PART VI
Selected Topics
703
CHAPTER 15
Chemistry and Periodic Trends among Metals
705
15.1 General Periodic Trends among Metals
15.2 Group 1 (IA)—The Alkali Metals
705
708
15.3 Group 2 (IIA)—The Alkaline Earth Metals
15.4 Group 11 (IB)—The Goinage Metals
718
724
15.5
15.6
15.7
15.8
15.9
15.10
Group 12 (IIB)—The Zinc Subgroup
Group .3 (IIIA)—The Scandium Family and Rare Earths
The Actinide Metals
Transition Metals, Groups 4 - 7 (IVA-VIIA)
Groups 8, 9. and 10 (Group VIII)
Compounds Containing Metal-Metal Bonds
729
732
737
738
747
751
General References
757
Problems
757
CHAPTER 16
Chemistry of Some Nonmetals
760
16.1
16.2
16.3
16.4
760
761
773
789
General Periodic Trends for Nonmetals
Nitrogen and Phosphorus
Oxygen, Sulfur, and Selenium
The Halogens
16.5 The Noble Gases
General References
Problems
807
812
813
CHAPTER 17
Cluster and Cage Compounds
816
17.1 Introduction
816
17.2 The Bonding Problem in Boranes
819
17.3
17.4
17.5
17.6
823
826
832
834
Structures of the Boron Hydrides
Molecular Orbital Description of Bonding in Boron Hydrides
Heteroboranes
Chemistry of the Boranes
xviii
Contents
17.7
17.8
17.9
17.10
Synthesis of Boron Hydrides
Carboranes
Some Chemistry of Group 13
Cluster Compounds
841
843
847
854
17.11 Electron-Precise Compounds and their Relation to Clusters
General References
Problems
877
879
880
CHAPTER 18
Bioinorganic Chemistry
888
18.1 Essential Elements
18.2 Oxygen Utilization
888
893
18.3 Supply and Storage of Iron
18.4 Oxidation—Reduction Processes
18.5 Metalloenzymes
901
905
910
18.6
18.7
18.8
18.9
919
922
924
926
927
928
Vitamin Bi 2
Nitrogenase
Photosynthesis
Roles of Na + , K + , Mg 2+ , Ca 2+ , and Ion Pumps
General References
Problems
APPENDIX A
Units
AI
APPENDIX B
Nomenclature of Inorganic Chemistry
B-l
APPENDIX C
Character Tables
C-l
APPENDIX D
Tanabe—Sugano Diagrams
Dl
APPENDIX E
Standard Half-Cell emf Data
El
INDEX
i-i