Inorganic Chemistry

by Miessler, Gary L.; Tarr, Donald A.

• ISBN13: 9780130354716
• ISBN10: 0130354716
• Edition: 3rd
• Format: Paperback
• Copyright: 2011-01-01
• Publisher: Prentice Hall

Summary

This highly readable book provides the essentials of Inorganic Chemistry with molecular symmetry as its foundation.Chapter topics include atomic structure, molecular orbitals, organometallic chemistry, simple bonding theory, symmetry and group theory, and more.For chemists and other professionals who want to update or improve their background in the field.

Table of Contents

Preface	xiii
Introduction to Inorganic Chemistry	1	(14)
What is Inorganic Chemistry?	1	(1)
Contrasts with Organic Chemistry	1	(4)
Genesis of the Elements (The Big Bang) and Formation of the Earth	5	(3)
Nuclear Reactions and Radioactivity	8	(1)
Distribution of Elements on Earth	9	(2)
The History of Inorganic Chemistry	11	(4)
Atomic Structure	15	(36)
Historical Development of Atomic Theory	15	(6)
The Periodic Table	16	(1)
Discovery of Subatomic Particles and the Bohr Atom	17	(4)
The Schrodinger Equation	21	(22)
The Particle in a Box	23	(2)
Quantum Numbers and Atomic Wave Functions	25	(9)
The Aufbau Principle	34	(4)
Shielding	38	(5)
Periodic Properties of Atoms	43	(8)
Ionization Energy	43	(1)
Electron Affinity	44	(1)
Covalent and Ionic Radii	44	(7)
Simple Bonding Theory	51	(25)
Lewis Electron-Dot Diagrams	51	(6)
Resonance	52	(1)
Expanded Shells	53	(1)
Formal Charge	53	(3)
Multiple Bonds in Be and B Compounds	56	(1)
Valence Shell Electron Pair Repulsion Theory	57	(10)
Lone Pair Repulsion	59	(3)
Multiple Bonds	62	(1)
Electronegativity and Atomic Size Effects	63	(3)
Ligand Close-Packing	66	(1)
Polar Molecules	67	(2)
Hydrogen Bonding	69	(7)
Symmetry and Group Theory	76	(40)
Symmetry Elements and Operations	76	(6)
Point Groups	82	(10)
Groups of Low and High Symmetry	84	(2)
Other Groups	86	(6)
Properties and Representations of Groups	92	(10)
Matrices	92	(2)
Representations of Point Groups	94	(3)
Character Tables	97	(5)
Examples and Applications of Symmetry	102	(14)
Chirality	102	(1)
Molecular Vibrations	103	(13)
Molecular Orbitals	116	(49)
Formation of Molecular Orbitals from Atomic Orbitals	116	(6)
Molecular Orbitals from s Orbitals	117	(2)
Molecular Orbitals from p Orbitals	119	(1)
Molecular Orbitals from d Orbitals	120	(2)
Nonbonding Orbitals and Other Factors	122	(1)
Homonuclear Diatomic Molecules	122	(12)
Molecular Orbitals	122	(2)
Orbital Mixing	124	(1)
First and Second Row Molecules	125	(5)
Photoelectron Spectroscopy	130	(2)
Correlation Diagrams	132	(2)
Heteronuclear Diatomic Molecules	134	(5)
Polar Bonds	134	(4)
Ionic Compounds and Molecular Orbitals	138	(1)
Molecular Orbitals for Larger Molecules	139	(22)
FHF	140	(3)
CO2	143	(5)
H2O	148	(3)
NH3	151	(3)
BF3	154	(3)
Molecular Shapes	157	(1)
Hybrid Orbitals	157	(4)
Expanded Shells and Molecular Orbitals	161	(4)
Acid-Base and Donor-Acceptor Chemistry	165	(42)
Acid-Base Concepts as Organizing Concepts	165	(1)
History	165	(1)
Major Acid-Base Concepts	166	(13)
Arrhenius Concept	166	(1)
Bronsted-Lowry Concept	167	(1)
Solvent System Concept	168	(2)
Lewis Concept	170	(1)
Frontier Orbitals and Acid-Base Reactions	171	(3)
Hydrogen Bonding	174	(4)
Electronic Spectra (Including Charge Transfer)	178	(1)
Hard and Soft Acids and Bases	179	(13)
Theory of Hard and Soft Acids and Bases	183	(4)
Quantitative Measures	187	(5)
Acid and Base Strength	192	(15)
Measurement of Acid-Base Interactions	192	(1)
Thermodynamic Measurements	193	(1)
Proton Affinity	194	(1)
Acidity and Basicity of Binary Hydrogen Compounds	194	(2)
Inductive Effects	196	(1)
Strength of Oxyacids	196	(1)
Acidity of Cations in Aqueous Solution	197	(2)
Steric Effects	199	(1)
Solvation and Acid-Base Strength	200	(1)
Nonaqueous Solvents and Acid-Base Strength	201	(2)
Superacids	203	(4)
The Crystalline Solid State	207	(33)
Formulas and Structures	207	(13)
Simple Structures	207	(7)
Structures of Binary Compounds	214	(4)
More Complex Compounds	218	(1)
Radius Ratio	218	(2)
Thermodynamics of Ionic Crystal Formation	220	(3)
Lattice Energy and Madelung Constant	220	(2)
Solubility, Ion Size (Large-Large and Small-Small), and HSAB	222	(1)
Molecular Orbitals and Band Structure	223	(5)
Diodes, The Photovoltaic Effect, and Light-Emitting Diodes	226	(2)
Superconductivity	228	(3)
Low-Temperature Superconducting Alloys	228	(1)
The Theory of Superconductivity (Cooper Pairs)	229	(1)
High-Temperature Superconductors (YBa2Cu3O7 and Related Compounds)	230	(1)
Bonding in Ionic Crystals	231	(1)
Imperfections in Solids	231	(1)
Silicates	232	(8)
Chemistry of the Main Group Elements	240	(59)
General Trends in Main Group Chemistry	241	(6)
Physical Properties	241	(2)
Electronegativity	243	(1)
Ionization Energy	244	(1)
Chemical Properties	244	(3)
Hydrogen	247	(2)
Chemical Properties	248	(1)
Group 1 (IA): The Alkali Metals	249	(4)
The Elements	249	(1)
Chemical Properties	250	(3)
Group 2 (IIA): The Alkaline Earths	253	(3)
The Elements	253	(1)
Chemical Properties	254	(2)
Group 13 (IIIA)	256	(5)
The Elements	256	(4)
Other Chemistry of the Group 13 (IIIA) Elements	260	(1)
Group 14 (IVA)	261	(11)
The Elements	261	(6)
Compounds	267	(5)
Group 15 (VA)	272	(7)
The Elements	272	(2)
Compounds	274	(5)
Group 16 (VIA)	279	(6)
The Elements	279	(6)
Group 17 (VIIA): The Halogens	285	(6)
The Elements	285	(6)
Group 18 (VIIIA): The Noble Gases	291	(8)
The Elements	291	(1)
Chemistry	292	(7)
Coordination Chemistry I: Structures and Isomers	299	(38)
History	299	(5)
Nomenclature	304	(5)
Isomerism	309	(14)
Stereoisomers	310	(1)
Four-Coordinate Complexes	310	(1)
Chirality	311	(1)
Six-Coordinate Complexes	311	(4)
Combinations of Chelate Rings	315	(3)
Ligand Ring Conformation	318	(1)
Constitutional Isomers	319	(3)
Experimental Separation and Identification of Isomers	322	(1)
Coordination Numbers and Structures	323	(14)
Low Coordination Numbers (CN = 1, 2, and 3)	325	(2)
Coordination Number 4	327	(1)
Coordination Number 5	328	(1)
Coordination Number 6	329	(2)
Coordination Number 7	331	(1)
Coordination Number 8	332	(1)
Larger Coordination Numbers	333	(4)
Coordination Chemistry II: Bonding	337	(42)
Experimental Evidence for Electronic Structures	337	(5)
Thermodynamic Data	337	(2)
Magnetic Susceptibility	339	(3)
Electronic Spectra	342	(1)
Coordination Numbers and Molecular Shapes	342	(1)
Theories of Electronic Structure	342	(3)
Terminology	342	(1)
Historical Background	343	(2)
Ligand Field Theory	345	(17)
Molecular Orbitals for Octahedral Complexes	345	(1)
Orbital Splitting and Electron Spin	346	(4)
Ligand Field Stabilization Energy	350	(2)
Pi Bonding	352	(4)
Square-Planar Complexes	356	(4)
Tetrahedral Complexes	360	(2)
Angular Overlap	362	(8)
Sigma-Donor Interactions	362	(2)
Pi-Acceptor Interactions	364	(2)
Pi-Donor Interactions	366	(1)
Types of Ligands and the Spectrochemical Series	367	(1)
Magnitudes of eσ, eπ, and Δ	368	(2)
The Jahn-Teller Effect	370	(3)
Four- and Six- Coordinate Preferences	373	(2)
Other Shapes	375	(4)
Coordination Chemistry III: Electronic Spectra	379	(33)
Absorption of Light	380	(2)
Beer-Lambert Absorption Law	380	(2)
Quantum Numbers of Multielectron Atoms	382	(6)
Spin-Orbit Coupling	387	(1)
Electronic Spectra of Coordination Compounds	388	(24)
Selection Rules	390	(1)
Correlation Diagrams	391	(2)
Tanabe-Sugano Diagrams	393	(5)
Jahn-Teller Distortions and Spectra	398	(3)
Examples of Applications of Tanabe-Sugano Diagrams: Determining Δ0 from Spectra	401	(5)
Tetrahedral Complexes	406	(1)
Charge-Transfer Spectra	407	(5)
Coordination Chemistry IV: Reactions and Mechanisms	412	(42)
History and Principles	412	(2)
Substitution Reactions	414	(3)
Inert and Labile Compounds	414	(1)
Mechanisms of Substitution	415	(2)
Kinetic Consequences of Reaction Pathways	417	(3)
Dissociation (D)	417	(1)
Interchange (I)	418	(1)
Association (A)	419	(1)
Experimental Evidence in Octahedral Substitution	420	(9)
Dissociation	420	(3)
Linear Free Energy Relationships	423	(2)
Associative Mechanisms	425	(1)
The Conjugate Base Mechanism	426	(2)
The Kinetic Chelate Effect	428	(1)
Stereochemistry of Reactions	429	(5)
Substitution in trans Complexes	430	(2)
Substitution in cis Complexes	432	(1)
Isomerization of Chelate Rings	433	(1)
Substitution Reactions of Square-Planar Complexes	434	(3)
Kinetics and Stereochemistry of Square-Planar Substitutions	434	(1)
Evidence for Associative Reactions	435	(2)
The trans Effect	437	(3)
Explanations of the trans Effect	439	(1)
Oxidation-Reduction Reactions	440	(6)
Inner-and Outer-Sphere Reactions	441	(4)
Conditions for High and Low Oxidation Numbers	445	(1)
Reactions of Coordinated Ligands	446	(8)
Hydrolysis of Esters, Amides, and Peptides	446	(2)
Template Reactions	448	(1)
Electrophilic Substitution	449	(5)
Organometallic Chemistry	454	(66)
Historical Background	457	(1)
Organic Ligands and Nomenclature	458	(2)
The 18-Electron Rule	460	(7)
Counting Electrons	460	(3)
Why 18 Electrons?	463	(2)
Square-Planar Complexes	465	(2)
Ligands in Organometallic Chemistry	467	(15)
Carbonyl (CO) Complexes	467	(8)
Ligands Similar to CO	475	(2)
Hydride and Dihydrogen Complexes	477	(2)
Ligands Having Extended π Systems	479	(3)
Bonding Between Metal Atoms and Organic Π Systems	482	(14)
Linear π Systems	482	(3)
Cyclic π Systems	485	(7)
Fullerene Complexes	492	(4)
Complexes Containing M---C, M = C, and M ≡ C Bonds	496	(7)
Alkyl and Related Complexes	496	(2)
Carbene Complexes	498	(3)
Carbyne (Alkylidyne) Complexes	501	(2)
Spectral Analysis and Characterization of Organometallic Complexes	503	(17)
Infrared Spectra	503	(4)
NMR Spectra	507	(2)
Examples of Characterization	509	(11)
Organometallic Reactions and Catalysis	520	(36)
Reactions Involving Gain or Loss of Ligands	520	(8)
Ligand Dissociation and Substitution	521	(3)
Oxidative Addition	524	(1)
Reductive Elimination	525	(1)
Nucleophilic Displacement	526	(2)
Reactions Involving Modification of Ligands	528	(6)
Insertion	528	(1)
Carbonyl Insertion (Alkyl Migration)	528	(5)
1,2 Insertions	533	(1)
Hydride Elimination	533	(1)
Abstraction	534	(1)
Organometallic Catalysts	534	(14)
Example of Catalysis: Catalytic Deuteration	535	(1)
Hydroformylation	535	(3)
Monsanto Acetic Acid Process	538	(3)
Wacker (Smidt) Process	541	(1)
Hydrogenation by Wilkinson's Catalyst	542	(2)
Olefin Metathesis	544	(4)
Heterogeneous Catalysts	548	(8)
Ziegler-Natta Polymerizations	548	(1)
Water Gas Reaction	549	(7)
Parallels Between Main Group and Organometallic Chemistry	556	(38)
Main Group Parallels with Binary Carbonyl Complexes	556	(2)
The Isolobal Analogy	558	(8)
Extensions of the Analogy	561	(4)
Examples of Applications of the Analogy	565	(1)
Metal-Metal Bonds	566	(6)
Multiple Metal-Metal Bonds	568	(4)
Cluster Compounds	572	(22)
Boranes	572	(5)
Heteroboranes	577	(2)
Metallaboranes and Metallacarboranes	579	(3)
Carbonyl Clusters	582	(5)
Carbide Clusters	587	(1)
Additional Comments on Clusters	588	(6)
Bioinorganic and Environmental Chemistry	594	(43)
Porphyrins and Related Complexes	596	(8)
Iron Porphyrins	597	(3)
Similar Ring Compounds	600	(4)
Other Iron Compounds	604	(2)
Zinc and Copper Enzymes	606	(5)
Nitrogen Fixation	611	(5)
Nitric Oxide	616	(2)
Inorganic Medicinal Compounds	618	(4)
Cisplatin and Related Complexes	618	(4)
Auranofin and Arthritis Treatment	622	(1)
Vanadium Complexes in Medicine	622	(1)
Study of DNA Using Inorganic Agents	622	(2)
Environmental Chemistry	624	(13)
Metals	624	(5)
Nonmetals	629	(8)
Appendix A Answers to Exercises	637	(31)
Appendix B-1 Ionic Radii	668	(3)
Appendix B-2 Ionization Energy	671	(1)
Appendix B-3 Electron Affinity	672	(1)
Appendix B-4 Electronegativity	673	(1)
Appendix B-5 Absolute Hardness Parameters	674	(1)
Appendix B-6 CA, EA, CB, and EB Values	675	(1)
Appendix B-7 Latimer Diagrams for Selected Elements	676	(5)
Appendix C Character Tables	681	(10)
Appendix D Electron-Dot Diagrams and Formal Charge	691	(6)
Index	697