Table of contents for Frontier orbitals : a practical manual / Nguyen Anh.

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CHAPTER I. What can we do with Frontier Orbitals?	
I. The advantages of the perturbation method	
II. The uses of frontier orbitals	
Five standard frontier orbital treatments of reactivity	
Three standard frontier orbital treatments of structural problems	
CHAPTER II. Atomic and molecular orbitals	
I. Atomic orbitals	
II. Molecular orbitals	
III. The MO?s of a homonuclear diatomic molecule	
1. Calculations	
2. A physical interpretation	
A. Molecular orbitals	
B. The parameters	
The Coulomb integral a	
The resonance integral b	
The overlap integral	
C. Mulliken analysis	
Overlap population	
Net atomic charges	14
IV. MO?s of a heteronuclear diatomic molecule	
1. Calculations	
2. A physical interpretation
V. p MO?s of polyatomic molecules	
1. The H¿ckel method for polyatomic molecules	
A. The H¿ckel method applied to the allyl system	
B. Coulson formulae for linear polyenes	
C. Bond orders and net charges	
2. How to calculate H¿ckel MO?s	
A. Choosing the parameters a end b	
Alkyl substituents	
The methyl inductive effect	
B. Writing the secular determinant	
C. Checking the calculations	
D. Electron counting	
To dig deeper	
CHAPTER III. The perturbation method	
I. Perturbations and H¿ckel methods	
II. Study of bimolecular reactions using perturbation methods	
1. Two orbital systems	
A. The MO?s in the starting materials are degenerate	
B. The MO?s in the starting materials are not degenerate	
2. Systems having more than two orbitals	
3. The frontier orbital approximation	
4. Unimolecular systems	
III. Perturbation theory: the practical aspects	
1. Numerical calculations	
2. Qualitative applications	
IV. The Dewar PMO method	
1. Alternant hydrocarbons	
The pairing theorem	34
2. The Dewar PMO method	
H¿ckel rule	
Generalized aromaticity rules	
Dewar-Zimmerman rule	
3. Advantages and disadvantages of the PMO method	
A. Advantages	
B. Disadvantages	
 To dig deeper	
CHAPTER IV. Absolute and relative reactivities	
I. Absolute reactivity	
1. Bimolecular reactions	
A. Cycloadditions	
B. Justification of the frontier orbital approximation	
2. Unimolecular reactions	
A. Sigmatropic reactions	
B. Electrocyclic reactions	
Limitations of the foregoing rules	
II. Relative reactivity	
1. Electrophilic reactions		
 Geometry of ?ate? complexes	
2. Nucleophilic reactions	
A. The nucleophilicity of halides	
B. Electrophilic assistance	
C. An example of chemoselectivity: relative reactivities of carbonyl compounds	
3. Cycloadditions	
 Alder?s rule	
III. Limitations of rules 1 and 2	
1. Some difficulties encountered with rule 1	
A. Cheletropic reactions	
Electron count in cheletropic reactions	
B. Systems having more than two components	
2. Problems with rule 2	
A. Apparent violations of rule 2	
The relative reactivities of alkenes and alkynes	
The relative reactivities of carbonyl compounds	
Staudinger reaction	
Exceptions and how to predict them	
B. Why overlap is ignored	
C. ?Formal? frontier orbitals and ?chemical? frontier orbitals	
CHAPTER V. Regioselectivity	
I. Cycloadditions	
II. Electrophilic reactions	
1. Markovnikov?s rule	
2. Regioselectivity involving enols and enolates	
Regioselectivity in sulfur compounds	
3. FO theory and ionic reactions	
FO study of ionic reactions using H¿ckel calculations	
FO study of ionic reactions using SCF methods	
FO theory and gas phase reactions	
III. Nucleophilic reactions	
Additions to conjugated carbonyl compounds	
IV. Radical reactions	
V. Periselectivity	
VI. Limitations of rule 3	
CHAPTER VI. Stereoselectivity	
I. Pericyclic reactions	
1. Electrocyclic reactions	
2. A. Torquoselectivity	
3. B. Extensions of the Rondan-Houk treatment and quantitative analyses	
Quantitative analyses	
C. An exercise in qualitative analysis	
2. Sigmatropic rearrangements	
A. Torquoselectivity	
B. Cope rearrangements	
3. Cycloadditions and their orientations	
A. Endo-exo orientation	
B. Syn-anti orientation	
II. Addition reactions	
1. Nucleophilic additions	
2. A. The non-perpendicular Dunitz-B¿rgi attack
B. Baldwin?s cyclization rules	
C. 1,2 asymmetric inductions	
The Cram and Felkin models	
The flattening rule	
The importance of being flexible	
Classification of substituents as L, M, S and the Cieplak model	
Karabatsos model	
D. Which factors control asymmetric induction?
E. Some recent models	
Houk model for electrophilic additions to alkenes	
Morokuma model for conjugated additions	
Radical additions to alkenes	
Evans electrostatic models for 1,2 and 1,3 asymmetric inductions	
The inside alkoxy effect	
2. Electrophilic additions	
3. Application to the aldol addition	
III. Substitution reactions	
1. Bimolecular electrophilic substitutions	
2. Bimolecular nucleophilic substitutions	
3. Application to the aldol addition	
IV. Limitations of rule 4	
CHAPTER VII. Some structural problems	
I. Principle of the method	
II. Stable conformations	
1. Aldehydes, alkenes and enol ethers	
A. Ethanal and propene	
B. Propanal and methyl vinyl ether	
C. Chloroethanal and 2-chloropropanal	
2. Conformations of some ions	
Walsh orbitals	
A. The cyclopropylcarbinyl cation	
B. Substituted ethyl ions	
The stereochemistry of vinylic SN2 reactions	
3. The anomeric effect	
A. Lone pairs in ethers	
B. The anomeric effect	
C. Applications	
D. A warning	
4. The geminal effect	
5. The gauche effect	
Two adjacent lone pairs	
A lone pair adjacent to a polar bond	
Two adjacent polar bonds	
III. Reactive conformations	
IV. How to stabilize inherently unstable species	
Stable carbenes	
V. Bonds with abnormal lengths	
1. Structural consequences of HOMO-LUMO interactions	
2. Applications to nucleophilic additions	
A. Additions and additions-eliminations	
B. Reversible and irreversible reactions. Multistep mechanisms	
3. Substituent effects	
A. Fragmentations, enolizations and related reactions	
Cleaving CC bonds	
Cleaving CH bonds	
B. The Cope reaction	
Substitutions at positions 3 and 4. The anionic oxy-Cope reaction	
Substitutions at other positions	
C. The Claisen reaction	
D. Substituted cyclopropanes	
VI. Abnormal valence angles	
CHAPTER VIII. Going further	
I. The limits of frontier orbital theory	
1. The simplifying hypotheses of frontier orbital theory	
2. Consequences	
Limitations imposed by approximation (1)	
Limitations imposed by approximation (2)	
Limitations imposed by approximation (3)	
Limitations imposed by approximation (4)	
Limitations imposed by approximation (5)	
II. The capabilities of computational chemistry	
1. Structural problems	
2. Reactivity problems	
3. Beyond potential surfaces	
III. The methods of quantum chemistry	
1. The approximations	
2. 2. The principal theoretical models	
A. Ab initio and semi-empirical models	
B. Basis sets	
C. Correlation models	
Configuration interaction models	
Moller-Plesset models	
DFT models	
D . Solvent effects	
3. A few technical points	
 Choosing the model	
 Choosing a basis set	
To dig deeper	
ANNEX. MO catalogue	
Summary table	

Library of Congress Subject Headings for this publication:

Molecular orbitals.
Chemistry, Physical organic.