Orbital interaction theory of organic chemistry /
Saved in:
| Author / Creator: | Rauk, Arvi, 1942- |
|---|---|
| Imprint: | New York : J. Wiley, c1994. |
| Description: | xv, 307 p. : ill. ; 25 cm. + 1 computer disk (3 1/2 in.) |
| Language: | English |
| Subject: | |
| Format: | Print Book |
| URL for this record: | http://pi.lib.uchicago.edu/1001/cat/bib/1603027 |
Table of Contents:
- Preface
- 1. Symmetry and Stereochemistry
- Purpose
- Definition of a Group
- Molecular Point Groups
- Schoenflies Notation
- Interrelations of Symmetry Elements
- Type Classification
- Isomerism and Measurements
- Stereoisomerism of Molecules
- Stereotopic Relationships of Groups in Molecules
- Asymmetric Synthesis and Stereochemistry
- NMR and Stereochemistry
- Symmetry and Structural Parameters
- Note on Hybridization
- Symmetry and Orbitals
- Atomic Orbitals
- Molecular and Group Orbitals
- In What Combination?
- 2. Molecular Orbital Theory
- Introduction
- Electronic Schrodinger Equation (A.1)
- Fock Equations (A.42)
- The Basis Set (STO-3G, 6-31G*, and All That)
- Orbital Energies and Orbitals
- Representation of MOs
- Total Energies and the Hartree-Fock Limit
- Successes and Failures of Hartree-Fock Theory
- Beyond Hartree-Fock
- Density Functional Theory
- Geometry Optimization
- Normal Coordinates and Harmonic Frequency Analysis
- Zero Point Vibrational Energies
- 3. Orbital Interaction Theory
- Relationship to Hartree-Fock Equations
- Huckel Approximation
- Orbital Energies and Total Electronic Energy
- Case Study of a Two-Orbital Interaction
- Case 1: [varepsilon subscript A] = [varepsilon subscript B], S[subscript AB] = 0
- Case 2: [varepsilon subscript A] = [varepsilon subscript B], S[subscript AB] ] 0, S[subscript AB] [angle quoation mark left] 1
- Case 3: [varepsilon subscript A] ] [varepsilon subscript B], S[subscript AB] = 0
- Case 4: [varepsilon subscript A] ] [varepsilon subscript B], S[subscript AB] ] 0
- Effect of Overlap
- Energetic Effect of Overlap
- Orbital Effect of Overlap
- First Look at Bonding
- Relationship to Perturbation Theory
- Generalizations for Intermolecular Interactions
- Energy and Charge Distribution Changes from Orbital Interaction
- Four-Electron, Two-Orbital Interaction
- Three-Electron, Two-Orbital Interaction
- Two-Electron, Two-Orbital Interaction
- One-Electron, Two-Orbital Interaction
- Zero-Electron, Two-Orbital Interaction
- Interactions between Molecules: Many Electrons, Many Orbitals
- General Principles Governing the Magnitude of h[subscript AB] and S[subscript AB]
- Interactions of MOs
- Electrostatic Effects
- Group Orbitals
- Zero-Coordinated Atoms
- Monocoordinated Atoms
- Dicoordinated Atoms
- Tricoordinated Atoms
- Tetracoordinated Atoms
- Assumptions for Application of Qualitative MO Theory
- Example: Carbonyl Group
- Construction of Interaction Diagram
- Interpretation of Interaction Diagram
- Chemical Reactivity
- Why Does It Work and When Might it Not?
- 4. Sigma Bonds and Orbital Interaction Theory
- C--X [sigma] Bonds: X = C, N, O, F and X = F, Cl, Br, I
- [sigma] Bonds: Homolytic versus Heterolytic Cleavage
- Heterolytic Cleavage of [sigma] Bonds Involving C or H
- Homolytic Cleavage of [sigma] Bonds Involving C or H
- Homonuclear [sigma] Bonds C--C, N--N, O--O, F--F, Cl--Cl, Br--Br, and I--I
- Interactions of [sigma] Bonds
- [sigma] Bonds as Electron Donors or Acceptors
- [sigma] Bonds as Electron Acceptors
- As a [sigma] Acceptor
- As a [pi] Acceptor
- [sigma] Bonds as Electron Donors
- As a [sigma] Donor
- As a [pi] Donor
- Bonding in Cyclopropane
- 5. Simple Huckel Molecular Orbital Theory
- Simple Huckel Assumptions
- Charge and Bond Order in SHMO Theory: (S[subscript AB] = 0, One Orbital per Atom
- Electron Population and Net Charge of Center A
- Bond Order between Centers A and B
- Factors Governing Energies of MOs: SHMO Theory
- Reference Energy and Energy Scale
- Heteroatoms in SHMO Theory
- Effect of Coordination Number on [alpha] and [beta]
- Hybridization at C in Terms of [alpha] and [beta]
- Gross Classification of Molecules on the Basis of MO Energies
- 6. Reactions and Properties of [pi] Bonds
- Reactions of Olefins (Alkenes)
- Effect of X: Substituents
- Effect of Z Substituents
- Effect of "C" Substituents
- Effect of Distortion of Molecular Skeleton
- Alkynes
- [pi] Bonds to and between Higher Row Elements
- [pi] Bonds to Silicon, Phosphorus, and Sulfur
- 7. Reactive Intermediates
- Reactive Intermediates [CH subscript 3 superscript +], [CH subscript 3 superscript -], [CH subscript 3 superscript .], and [:CH subscript 2]
- Carbocations
- Intermolecular Reactions of Carbocations
- Intramolecular Reactions of Carbocations
- Silyl Cations
- Carbanions
- Carbon Free Radicals
- Carbenes
- Nitrenes and Nitrenium Ions
- Nitrenes
- Nitrenium Ions
- 8. Carbonyl Compounds
- Reactions of Carbonyl Compounds
- Electrophilic Attack on a Carbonyl Group
- Basicity and Nucleophilicity of the Oxygen Atom
- Nucleophilic Attack on a Carbonyl Group
- Amide Group
- Thermodynamic Stability of Substituted Carbonyl Groups
- 9. Nucleophilic Substitution Reactions
- Nucleophilic Substitution at Saturated Carbon
- Unimolecular Nucleophilic Substitution S[subscript N]1
- Bimolecular Nucleophilic Substitution S[subscript N]2
- Another Description of the S[subscript N]2 Reaction: VBCM Model
- 10. Bonds to Hydrogen
- Hydrogen Bonds and Proton Abstraction Reactions
- Hydrogen Bonds
- Symmetrical and Bifurcated Hydrogen Bonds
- Proton Abstraction Reactions
- E2 Elimination Reaction
- E1cB Mechanism Reaction
- E1 Elimination Reaction
- Reaction with Electrophiles: Hydride Abstraction and Hydride Bridging
- Activation by [pi] Donors (X: and "C" Substituents)
- Hydride Abstraction
- Hydride Bridges
- Reaction with Free Radicals: Hydrogen Atom Abstraction and One- or Three-Electron Bonding
- Hydrogen-Bridged Radicals
- Hydrogen Atom Transfer
- 11. Aromatic Compounds
- Reactions of Aromatic Compounds
- Cyclic [pi] Systems by Simple Huckel MO Theory
- Aromaticity in [sigma]-Bonded Arrays?
- Reactions of substituted Benzenes
- Electrophilic Substitutions
- Effect of Substituents on Substrate Reactivity
- Electrophilic Attack on X:-Substituted Benzenes
- Electrophilic Attack on Z-Substituted Benzenes
- Electrophilic Attack on "C"-Substituted Benzenes
- Electrophilic Attack on N Aromatics: Pyrrole and Pyridine
- Nucleophilic Substitutions
- Effect of Substituents on Substrate Reactivity
- Nucleophilic Attack on Z-Substituted Benzenes
- Nucleophilic Attack on N Aromatics: Pyrrole and Pyridine
- Nucleophilic Substitution by Proton Abstraction
- 12. Pericyclic Reactions
- General Considerations
- Cycloadditions and Cycloreversions
- Stereochemical Considerations
- Electrocyclic Reactions
- Stereochemical Considerations
- Cheletropic Reactions
- Stereochemical Considerations
- Sigmatropic Rearrangements
- Stereochemical Considerations
- Component Analysis (Allowed or Forbidden?)
- Rule for Component Analysis
- Diels-Alder Reaction
- Cope Rearrangement
- 1,3-Dipolar Cycloaddition Reactions
- 13. Organometallic Compounds
- Transition Metals
- Ligands in Transition Metal Complexes
- Orbitals in Transition Metal Bonding
- Orbital Energies
- Valence Orbitals of Reactive Metal Complexes
- Six Valence Orbitals of Tricoordinated Metal
- Five Valence Orbitals of Tetracoordinated Metal
- Four Valence Orbitals of Pentacoordinated Structure
- Transition Metals and C--H or H--H Sigma Bonds
- More About C Ligands in Transition Metal Complexes
- Chelating Ligands
- Organic [pi]-Bonded Molecules as Ligands
- Transition Metal Bonding to Alkenes: Zeise's Salt
- Agostic Interaction
- Ziegler-Natta Polymerization
- Oxidative Addition to H--H and C--H Bonds
- 14. Orbital and State Correlation Diagrams
- General Principles
- Woodward-Hoffman Orbital Correlation Diagrams
- Cycloaddition Reactions
- Electrocyclic Reactions
- Cheletropic Reactions
- Photochemistry from Orbital Correlation Diagrams
- Limitations of Orbital Correlation Diagrams
- State Correlation Diagrams
- Electronic States from MOs
- Rules for Correlation of Electronic States
- Example: Carbene Addition to an Olefin
- 15. Photochemistry
- Photoexcitation
- Jablonski Diagram
- Fate of Excited Molecule in Solution
- Dauben-Salem-Turro Analysis
- Norrish Type II Reaction of Carbonyl Compounds
- Norrish Type I Cleavage Reaction of Carbonyl Compounds
- Appendix A. Derivation of Hartree-Fock Theory
- Electronic Hamiltonian Operator
- Electronic Schrodinger Equation
- Expectation Values
- Many-Electron Wave Function
- Electronic Hartree-Fock Energy
- Variation of E[subscript HF]
- LCAO Solution of Fock Equations
- Integrals
- The Basis Set (STO-3G, 6-31G*, and All That)
- Interpretation of Solutions of HF Equations
- Orbital Energies and Total Electronic Energy
- Restricted Hartree-Fock Theory
- Mulliken Population Analysis
- Dipole Moments
- Total Energies
- Configuration Energies
- Post-Hartree-Fock Methods
- Configuration Interaction Theory
- Excited States from CI Calculations
- Many-Body Perturbation Theory
- Rayleigh-Schrodinger Perturbation Theory
- Moller-Plesset Perturbation Theory
- Density Functional Theory
- Appendix B. Exercises
- Chapter 1
- Chapter 2 and Appendix A
- Chapter 3
- Chapter 4
- Chapter 5
- Chapter 6
- Chapter 7
- Chapter 8
- Chapter 9
- Chapter 10
- Chapter 11
- Chapter 12
- Chapter 13
- Chapter 14
- Chapter 15
- Miscellaneous
- References and Notes
- Index
