The PMO Theory of Organic Chemistry

1. Introduction to MO Theory.- 1.1. The Hydrogen Atom; Orbits and Orbitals.- 1.2. The Orbital Approximation; Helium.- 1.3. Lithium; the Pauli Principle.- 1.4. The Atoms Be-Ne; Hund's Rule.- 1.5. The Hydrogen Molecule; Molecular Orbitals.- 1.6. The Born-Oppenheimer Approximation.- 1.7. HHe +, HHe, and HLi; Perturbation Theory.- 1.8. Methane; Symmetry Orbitals.- 1.9. Photoelectron Spectroscopy and Ionization Potentials.- 1.10. Methane, Continued; Hybridization and Localized Bonds.- 1.11. Diatomic Molecules.- 1.12. The Paraffins; Localized Bonds.- 1.13. Ethylene; ? Bonds.- 1.14. Acetylene.- 1.15. Breakdown of the Localized Bond Model: Three-Center Bonds, Conjugated Molecules, and Reaction Intermediates.- 1.16. Relationships between Different Types of Delocalized Systems.- 1.17. Summary.- Problems.- Selected Reading.- References.- 2. Perturbation Theory.- 2.1. The Usefulness of Perturbation Theory.- 2.2. Types of Perturbations Involved in the Comparison of Conjugated Systems.- 2.3. Monocentric Perturbations.- 2.4. Intramolecular Union.- 2.5. Intermolecular Union.- 2.6. Multiple Union; Additivity of Perturbations.- Problems.- Selected Reading.- Reference.- 3. PMO Treatment of Conjugated System.- 3.1. Principles of the PMO Method; Alternant and Nonalternant Systems.- 3.2. The Pairing Theorem.- 3.3. Calculation of NBMO Coefficients.- 3.4. Distribution of Formal Charges in AHs.- 3.5. Monocentric Perturbations; Correlation of Isoconjugate Systems.- 3.6. Intermolecular Union of Even AHs.- 3.7. Multiple Union of Even AHs.- 3.8. Union of Odd AHs.- 3.9. Alternation of Bonds in Polyenes.- 3.10. Even Monocyclic Polyenes; Aromaticity and Antiaromaticity; Hückel's Rule.- 3.11. Bond Alternation in Annulenes.- 3.12. Polycyclic Polyenes.- 3.13. Intramolecular Union; Monocyclic Nonalternant Hydrocarbons.- 3.14. Essential Single and Double Bonds; General Rules for Aromaticity.- 3.15. Significance of Classical Valence Structures.- 3.16. Union of an Odd AH with an Even AH.- 3.17. Hückel and Anti-Hückel Systems.- 3.18. Effect of Heteroatoms.- 3.19. Polarization of ? Electrons.- 3.20. Stereochemistry of Nitrogen.- 3.21. Resonance Theory in the Light of the PMO Method.- Appendix. ? Energy of Union of Even AHs.- Problems.- Selected Reading.- 4. Chemical Equilibrium.- 4.1. Basic Principles.- 4.2. Factors Contributing to the Energy of Reaction.- 4.3. Reaction of AHs.- 4.4. Electron Transfer Processes; Redox Potentials.- 4.5. Nonalternant Systems.- 4.6. Effect of Heteroatoms.- 4.7. The ?-Inductive Effect.- 4.8. Classification of Substituents.- 4.9. Inductive (I) Substituents.- 4.10. Electromeric Substituents; ± E Substituents.- 4.11. + E Substituents.- 4.12. - E Substituents.- 4.13. Summary of Substituent Effects.- 4.14. Cross-Conjugation.- 4.15. Mutual Conjugation.- 4.16. The Field Effect.- 4.17. The Hammett Equation.- Problems.- Selected Reading.- References.- 5. Chemical Reactivity.- 5.1. Basic Principles.- 5.2. The Transition State Theory.- 5.3. Transition States for Aliphatic Substitution.- 5.4. Reaction Paths and Reaction Coordinates.- 5.5. The Bell-Evans-Polanyi (BEP) Principle; Relationships between Rates of Reactions and Corresponding Equilibrium Constants.- 5.6. Reactions Where Intermediates Are Involved.- 5.7. Solvent Effects; Electrostatic Interactions and the Hellman-Feynman Theorem.- 5.8. Limitations of the BEP Principle.- 5.9. Classification of Reactions.- 5.10. Prototropic Reactions of ISOB Type.- 5.11. Prototropic Reactions of EOB Type.- 5.12. Nucleophilic Aliphatic Substitution.- A. SN1 Reactions.- B. SN2 Reactions.- 5.13. Nucleophilicity and Basicity.- 5.14. Electrophilic Aliphatic Substitution.- 5.15. Radical Substitution Reactions (EOB ).- 5.16. Elimination Reactions.- 5.17. ?-Complex Reactions (E?B ).- 5.18. Electrophilic Addition (E?B and EOB ).- 5.19. ? Complexes vs. Three-Membered Rings.- 5.20. Nucleophilic Addition and Related Reactions (EOB ).- 5.21. Radical Addition and Polymerization (EOB ).- 5.22. Aromatic Substitution in Even Systems (EOB ).- 5.23. Substitution vs. Addition.- 5.24. Neighboring Group Participation.- 5.25. Some OE Reactions.- 5.26. Thermal Pericyclic Reactions (EEA and OOA ).- 5.27. Examples of Pericyclic Reactions.- A. Cycloaddition Reactions (EEA and OOA ).- B. Some Special Features of the Diels-Alder Reaction.- C. Sigmatropic Reactions (EEA and OOA ).- D. Electrocyclic Reactions.- E. Chelotropic Reactions.- 5.28. Alternative Derivations of the Woodward-Hoffman Rules. "Allowed" and "Forbidden" Pericyclic Reactions.- 5.29. Catalysis of Pericyclic Reactions by Transition Metals.- 5.30. Reactions Involving Biradical Intermediates (ERA ).- 5.31. The ± E Substituent Technique.- Problems.- Selected Reading.- References.- 6. Light Absorption and Photochemistry.- 6.1. Introduction.- 6.2. The Nature of Electronically Excited States.- 6.3. The Franck-Condon Principle.- 6.4. Singlet and Triplet States.- 6.5. Extinction Coefficients and Transition Moments.- 6.6. Excitation and Deexcitation; Lifetimes of States, Fluorescence, and Phosphorescence.- 6.7. Excitation Energies of Even AHs.- 6.8. Excitation Energies of Odd AHs.- 6.9. ? ? ?* and n ??* in Even, Heteroconjugated Systems.- 6.10. ? ? ?* Transitions in Odd, Heteroconjugated Systems.- 6.11. Effect of Substituents on Light Absorption.- 6.12. Basic Principles of Photochemistry; Types of Photochemical Process.- 6.13. The Role of the Born-Oppenheimer (BO) Approximation.- 6.14. The Role of Antibonding Electrons.- 6.15. Classification of Photochemical Reactions.- 6.16. Examples of Photochemical Reactions.- A. X-Type Reactions.- B. GR Reactions.- C. G1 Reactions.- D. GN Reactions.- E. GA Reactions.- 6.17. Chemiluminescent Reactions.- 6.18. Summary.- Problems.- Selected Reading.- References.- 7. Reactions of Transient Ions.- 7.1. Ions in the Gas Phase; the Mass Spectrometer and Ion Cyclotron Spectroscopy.- 7.2. The Structure of Radical Ions.- 7.3. Reaction of Cation Radicals.- A. Cleavage Reactions.- B. Internal Displacement Reactions.- C. Pericyclic Reactions.- 7.4. Radical Anions in the Gas Phase.- 7.5. Ion-Molecule Reactions in the Gas Phase.- 7.6. Radical Cations in Solution.- A. Oxidation by Electron Transfer.- B. Electrochemical (Anodic) Oxidation.- C. Photochemical and Radiochemical Oxidation.- 7.7. Radical Anions in Solution.- 7.7 Problems.- 7.7 Selected Reading.- 7.7 References.- Answers to Selected Problems.