Inorganic Chemistry

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ISBN: 9780130354716 | 0130354716
Cover: Paperback
Copyright: 1/1/2011

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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.

Preface

xiii

Introduction to Inorganic Chemistry

(14)

What is Inorganic Chemistry?

(1)

Contrasts with Organic Chemistry

(4)

Genesis of the Elements (The Big Bang) and Formation of the Earth

(3)

Nuclear Reactions and Radioactivity

(1)

Distribution of Elements on Earth

(2)

The History of Inorganic Chemistry

(4)

Atomic Structure

(36)

Historical Development of Atomic Theory

(6)

The Periodic Table

(1)

Discovery of Subatomic Particles and the Bohr Atom

(4)

The Schrodinger Equation

(22)

The Particle in a Box

(2)

Quantum Numbers and Atomic Wave Functions

(9)

The Aufbau Principle

(4)

Shielding

(5)

Periodic Properties of Atoms

(8)

Ionization Energy

(1)

Electron Affinity

(1)

Covalent and Ionic Radii

(7)

Simple Bonding Theory

(25)

Lewis Electron-Dot Diagrams

(6)

Resonance

(1)

Expanded Shells

(1)

Formal Charge

(3)

Multiple Bonds in Be and B Compounds

(1)

Valence Shell Electron Pair Repulsion Theory

(10)

Lone Pair Repulsion

(3)

Multiple Bonds

(1)

Electronegativity and Atomic Size Effects

(3)

Ligand Close-Packing

(1)

Polar Molecules

(2)

Hydrogen Bonding

(7)

Symmetry and Group Theory

(40)

Symmetry Elements and Operations

(6)

Point Groups

(10)

Groups of Low and High Symmetry

(2)

Other Groups

(6)

Properties and Representations of Groups

(10)

Matrices

(2)

Representations of Point Groups

(3)

Character Tables

(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

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Inorganic Chemistry

Summary

Table of Contents

Supplemental Materials