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Orbital Interaction Theory of Organic Chemistry

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ISBN-10: 0471593893

ISBN-13: 9780471593898

Edition: 1st 1994

Authors: Arvi Rauk

List price: $82.50
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Book details

List price: $82.50
Edition: 1st
Copyright year: 1994
Publisher: John Wiley & Sons, Incorporated
Publication date: 3/22/1994
Binding: Hardcover
Pages: 336
Size: 6.50" wide x 9.75" long x 0.75" tall
Weight: 1.430
Language: English

ARVI RAUK, PhD, is Professor Emeritus in the Department of Chemistry at the University of Calgary in Calgary, Canada.

Preface
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?
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
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?
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
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
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
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
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
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
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
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
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
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
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
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
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
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