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A practical introduction to orbital interaction theory and its applications in modern organic chemistry Orbital interaction theory is a conceptual construct that lies at the very heart of modern organic chemistry. Comprising a comprehensive set of principles for explaining chemical reactivity, orbital interaction theory originates in a rigorous theory of electronic structure that also provides the basis for the powerful computational models and techniques with which chemists seek to describe and exploit the structures and thermodynamic and kinetic stabilities of molecules. Orbital Interaction Theory of Organic Chemistry, Second Edition introduces students to the fascinating world of organic chemistry at the mechanistic level with a thoroughly self-contained, well-integrated exposition of orbital interaction theory and its applications in modern organic chemistry. Professor Rauk reviews the concepts of symmetry and orbital theory, and explains reactivity in common functional groups and reactive intermediates in terms of orbital interaction theory. Aided by numerous examples and worked problems, he guides readers through basic chemistry concepts, such as acid and base strength, nucleophilicity, electrophilicity, and thermal stability (in terms of orbital interactions), and describes various computational models for describing those interactions. Updated and expanded, this latest edition of Orbital Interaction Theory of Organic Chemistry includes a completely new chapter on organometallics, increased coverage of density functional theory, many new application examples, and worked problems. The text is complemented by an interactive computer program that displays orbitals graphically and is available through a link to a Web site. Orbital Interaction Theory of Organic Chemistry, Second Edition is an excellent text for advanced-level undergraduate and graduate students in organic chemistry. It is also a valuable working resource for professional chemists seeking guidance on interpreting the quantitative data produced by modern computational chemists.

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• Preface(p. xiii)
• 1 Symmetry and Stereochemistry(p. 1)
• Purpose(p. 1)
• Definition of a Group(p. 2)
• Molecular Point Groups(p. 2)
• Schoenflies Notation(p. 2)
• Interrelations of Symmetry Elements(p. 3)
• Type Classification(p. 3)
• Isomerism and Measurements(p. 6)
• Stereoisomerism of Molecules(p. 8)
• Stereotopic Relationships of Groups in Molecules(p. 9)
• Asymmetric Synthesis and Stereochemistry(p. 10)
• NMR and Stereochemistry(p. 12)
• Symmetry and Structural Parameters(p. 14)
• Note on Hybridization(p. 15)
• Symmetry and Orbitals(p. 16)
• Atomic Orbitals(p. 16)
• Molecular and Group Orbitals(p. 17)
• In What Combination?(p. 19)
• 2 Molecular Orbital Theory(p. 20)
• Introduction(p. 20)
• Electronic Schrodinger Equation (A.1)(p. 21)
• Fock Equations (A.42)(p. 23)
• The Basis Set (STO-3G, 6-31G*, and All That)(p. 24)
• Orbital Energies and Orbitals(p. 25)
• Representation of MOs(p. 27)
• Total Energies and the Hartree-Fock Limit(p. 29)
• Successes and Failures of Hartree-Fock Theory(p. 29)
• Beyond Hartree-Fock(p. 30)
• Density Functional Theory(p. 31)
• Geometry Optimization(p. 31)
• Normal Coordinates and Harmonic Frequency Analysis(p. 32)
• Zero Point Vibrational Energies(p. 33)
• 3 Orbital Interaction Theory(p. 34)
• Relationship to Hartree-Fock Equations(p. 34)
• Huckel Approximation(p. 34)
• Orbital Energies and Total Electronic Energy(p. 34)
• Case Study of a Two-Orbital Interaction(p. 35)
• Case 1: [varepsilon subscript A] = [varepsilon subscript B], S[subscript AB] = 0(p. 38)
• Case 2: [varepsilon subscript A] = [varepsilon subscript B], S[subscript AB] ] 0, S[subscript AB] [angle quoation mark left] 1(p. 39)
• Case 3: [varepsilon subscript A] ] [varepsilon subscript B], S[subscript AB] = 0(p. 40)
• Case 4: [varepsilon subscript A] ] [varepsilon subscript B], S[subscript AB] ] 0(p. 42)
• Effect of Overlap(p. 44)
• Energetic Effect of Overlap(p. 44)
• Orbital Effect of Overlap(p. 44)
• First Look at Bonding(p. 45)
• Relationship to Perturbation Theory(p. 45)
• Generalizations for Intermolecular Interactions(p. 46)
• Energy and Charge Distribution Changes from Orbital Interaction(p. 47)
• Four-Electron, Two-Orbital Interaction(p. 47)
• Three-Electron, Two-Orbital Interaction(p. 48)
• Two-Electron, Two-Orbital Interaction(p. 49)
• One-Electron, Two-Orbital Interaction(p. 51)
• Zero-Electron, Two-Orbital Interaction(p. 51)
• Interactions between Molecules: Many Electrons, Many Orbitals(p. 52)
• General Principles Governing the Magnitude of h[subscript AB] and S[subscript AB](p. 52)
• Interactions of MOs(p. 52)
• Electrostatic Effects(p. 55)
• Group Orbitals(p. 56)
• Zero-Coordinated Atoms(p. 56)
• Monocoordinated Atoms(p. 57)
• Dicoordinated Atoms(p. 58)
• Tricoordinated Atoms(p. 59)
• Tetracoordinated Atoms(p. 59)
• Assumptions for Application of Qualitative MO Theory(p. 61)
• Example: Carbonyl Group(p. 62)
• Construction of Interaction Diagram(p. 62)
• Interpretation of Interaction Diagram(p. 65)
• Chemical Reactivity(p. 66)
• Why Does It Work and When Might it Not?(p. 69)
• 4 Sigma Bonds and Orbital Interaction Theory(p. 72)
• C--X [sigma] Bonds: X = C, N, O, F and X = F, Cl, Br, I(p. 72)
• [sigma] Bonds: Homolytic versus Heterolytic Cleavage(p. 74)
• Heterolytic Cleavage of [sigma] Bonds Involving C or H(p. 74)
• Homolytic Cleavage of [sigma] Bonds Involving C or H(p. 75)
• Homonuclear [sigma] Bonds C--C, N--N, O--O, F--F, Cl--Cl, Br--Br, and I--I(p. 76)
• Interactions of [sigma] Bonds(p. 77)
• [sigma] Bonds as Electron Donors or Acceptors(p. 81)
• [sigma] Bonds as Electron Acceptors(p. 81)
• As a [sigma] Acceptor(p. 81)
• As a [pi] Acceptor(p. 82)
• [sigma] Bonds as Electron Donors(p. 83)
• As a [sigma] Donor(p. 83)
• As a [pi] Donor(p. 84)
• Bonding in Cyclopropane(p. 84)
• 5 Simple Huckel Molecular Orbital Theory(p. 86)
• Simple Huckel Assumptions(p. 86)
• Charge and Bond Order in SHMO Theory: (S[subscript AB] = 0, One Orbital per Atom(p. 91)
• Electron Population and Net Charge of Center A(p. 91)
• Bond Order between Centers A and B(p. 92)
• Factors Governing Energies of MOs: SHMO Theory(p. 92)
• Reference Energy and Energy Scale(p. 92)
• Heteroatoms in SHMO Theory(p. 93)
• Effect of Coordination Number on [alpha] and [beta](p. 93)
• Hybridization at C in Terms of [alpha] and [beta](p. 96)
• Gross Classification of Molecules on the Basis of MO Energies(p. 96)
• 6 Reactions and Properties of [pi] Bonds(p. 98)
• Reactions of Olefins (Alkenes)(p. 98)
• Effect of X: Substituents(p. 99)
• Effect of Z Substituents(p. 101)
• Effect of "C" Substituents(p. 101)
• Effect of Distortion of Molecular Skeleton(p. 102)
• Alkynes(p. 103)
• [pi] Bonds to and between Higher Row Elements(p. 103)
• [pi] Bonds to Silicon, Phosphorus, and Sulfur(p. 103)
• 7 Reactive Intermediates(p. 105)
• Reactive Intermediates [CH subscript 3 superscript +], [CH subscript 3 superscript -], [CH subscript 3 superscript .], and [:CH subscript 2](p. 105)
• Carbocations(p. 105)
• Intermolecular Reactions of Carbocations(p. 106)
• Intramolecular Reactions of Carbocations(p. 107)
• Silyl Cations(p. 108)
• Carbanions(p. 108)
• Carbon Free Radicals(p. 110)
• Carbenes(p. 114)
• Nitrenes and Nitrenium Ions(p. 116)
• Nitrenes(p. 116)
• Nitrenium Ions(p. 118)
• 8 Carbonyl Compounds(p. 121)
• Reactions of Carbonyl Compounds(p. 121)
• Electrophilic Attack on a Carbonyl Group(p. 121)
• Basicity and Nucleophilicity of the Oxygen Atom(p. 122)
• Nucleophilic Attack on a Carbonyl Group(p. 124)
• Amide Group(p. 126)
• Thermodynamic Stability of Substituted Carbonyl Groups(p. 127)
• 9 Nucleophilic Substitution Reactions(p. 129)
• Nucleophilic Substitution at Saturated Carbon(p. 129)
• Unimolecular Nucleophilic Substitution S[subscript N]1(p. 129)
• Bimolecular Nucleophilic Substitution S[subscript N]2(p. 130)
• Another Description of the S[subscript N]2 Reaction: VBCM Model(p. 134)
• 10 Bonds to Hydrogen(p. 137)
• Hydrogen Bonds and Proton Abstraction Reactions(p. 137)
• Hydrogen Bonds(p. 137)
• Symmetrical and Bifurcated Hydrogen Bonds(p. 139)
• Proton Abstraction Reactions(p. 141)
• E2 Elimination Reaction(p. 143)
• E1cB Mechanism Reaction(p. 144)
• E1 Elimination Reaction(p. 144)
• Reaction with Electrophiles: Hydride Abstraction and Hydride Bridging(p. 145)
• Activation by [pi] Donors (X: and "C" Substituents)(p. 145)
• Hydride Abstraction(p. 145)
• Hydride Bridges(p. 147)
• Reaction with Free Radicals: Hydrogen Atom Abstraction and One- or Three-Electron Bonding(p. 147)
• Hydrogen-Bridged Radicals(p. 147)
• Hydrogen Atom Transfer(p. 148)
• 11 Aromatic Compounds(p. 150)
• Reactions of Aromatic Compounds(p. 150)
• Cyclic [pi] Systems by Simple Huckel MO Theory(p. 150)
• Aromaticity in [sigma]-Bonded Arrays?(p. 151)
• Reactions of substituted Benzenes(p. 152)
• Electrophilic Substitutions(p. 152)
• Effect of Substituents on Substrate Reactivity(p. 153)
• Electrophilic Attack on X:-Substituted Benzenes(p. 153)
• Electrophilic Attack on Z-Substituted Benzenes(p. 154)
• Electrophilic Attack on "C"-Substituted Benzenes(p. 155)
• Electrophilic Attack on N Aromatics: Pyrrole and Pyridine(p. 155)
• Nucleophilic Substitutions(p. 157)
• Effect of Substituents on Substrate Reactivity(p. 158)
• Nucleophilic Attack on Z-Substituted Benzenes(p. 158)
• Nucleophilic Attack on N Aromatics: Pyrrole and Pyridine(p. 158)
• Nucleophilic Substitution by Proton Abstraction(p. 159)
• 12 Pericyclic Reactions(p. 161)
• General Considerations(p. 161)
• Cycloadditions and Cycloreversions(p. 162)
• Stereochemical Considerations(p. 162)
• Electrocyclic Reactions(p. 165)
• Stereochemical Considerations(p. 165)
• Cheletropic Reactions(p. 165)
• Stereochemical Considerations(p. 165)
• Sigmatropic Rearrangements(p. 166)
• Stereochemical Considerations(p. 166)
• Component Analysis (Allowed or Forbidden?)(p. 167)
• Rule for Component Analysis(p. 168)
• Diels-Alder Reaction(p. 169)
• Cope Rearrangement(p. 170)
• 1,3-Dipolar Cycloaddition Reactions(p. 171)
• 13 Organometallic Compounds(p. 175)
• Transition Metals(p. 175)
• Ligands in Transition Metal Complexes(p. 176)
• Orbitals in Transition Metal Bonding(p. 176)
• Orbital Energies(p. 178)
• Valence Orbitals of Reactive Metal Complexes(p. 179)
• Six Valence Orbitals of Tricoordinated Metal(p. 182)
• Five Valence Orbitals of Tetracoordinated Metal(p. 182)
• Four Valence Orbitals of Pentacoordinated Structure(p. 185)
• Transition Metals and C--H or H--H Sigma Bonds(p. 186)
• More About C Ligands in Transition Metal Complexes(p. 186)
• Chelating Ligands(p. 187)
• Organic [pi]-Bonded Molecules as Ligands(p. 187)
• Transition Metal Bonding to Alkenes: Zeise's Salt(p. 187)
• Agostic Interaction(p. 191)
• Ziegler-Natta Polymerization(p. 192)
• Oxidative Addition to H--H and C--H Bonds(p. 194)
• 14 Orbital and State Correlation Diagrams(p. 196)
• General Principles(p. 196)
• Woodward-Hoffman Orbital Correlation Diagrams(p. 197)
• Cycloaddition Reactions(p. 197)
• Electrocyclic Reactions(p. 198)
• Cheletropic Reactions(p. 201)
• Photochemistry from Orbital Correlation Diagrams(p. 201)
• Limitations of Orbital Correlation Diagrams(p. 203)
• State Correlation Diagrams(p. 203)
• Electronic States from MOs(p. 205)
• Rules for Correlation of Electronic States(p. 206)
• Example: Carbene Addition to an Olefin(p. 206)
• 15 Photochemistry(p. 209)
• Photoexcitation(p. 209)
• Jablonski Diagram(p. 210)
• Fate of Excited Molecule in Solution(p. 211)
• Dauben-Salem-Turro Analysis(p. 212)
• Norrish Type II Reaction of Carbonyl Compounds(p. 213)
• Norrish Type I Cleavage Reaction of Carbonyl Compounds(p. 215)
• Appendix A Derivation of Hartree-Fock Theory(p. 218)
• Electronic Hamiltonian Operator(p. 218)
• Electronic Schrodinger Equation(p. 220)
• Expectation Values(p. 221)
• Many-Electron Wave Function(p. 221)
• Electronic Hartree-Fock Energy(p. 222)
• Variation of E[subscript HF](p. 226)
• LCAO Solution of Fock Equations(p. 229)
• Integrals(p. 231)
• The Basis Set (STO-3G, 6-31G*, and All That)(p. 232)
• Interpretation of Solutions of HF Equations(p. 233)
• Orbital Energies and Total Electronic Energy(p. 233)
• Restricted Hartree-Fock Theory(p. 234)
• Mulliken Population Analysis(p. 236)
• Dipole Moments(p. 236)
• Total Energies(p. 237)
• Configuration Energies(p. 237)
• Post-Hartree-Fock Methods(p. 239)
• Configuration Interaction Theory(p. 239)
• Excited States from CI Calculations(p. 241)
• Many-Body Perturbation Theory(p. 241)
• Rayleigh-Schrodinger Perturbation Theory(p. 241)
• Moller-Plesset Perturbation Theory(p. 244)
• Density Functional Theory(p. 245)
• Appendix B Exercises(p. 247)
• Chapter 1(p. 247)
• Chapter 2 and Appendix A(p. 249)
• Chapter 3(p. 252)
• Chapter 4(p. 262)
• Chapter 5(p. 264)
• Chapter 6(p. 272)
• Chapter 7(p. 273)
• Chapter 8(p. 278)
• Chapter 9(p. 281)
• Chapter 10(p. 281)
• Chapter 11(p. 284)
• Chapter 12(p. 288)
• Chapter 13(p. 292)
• Chapter 14(p. 296)
• Chapter 15(p. 298)
• Miscellaneous(p. 301)
• References and Notes(p. 313)
• Index(p. 325)

Reseñas proporcionadas por Syndetics

CHOICE Review

Rauk clearly examines and explains a rather wide variety of organic chemical reactions through a primarily qualitative application of molecular orbital interaction theory. The first five chapters (approximately half the book) present the fundamental concepts of symmetry and orbital theory necessary for an understanding of the material that follows. The second half utilizes orbital interaction theory to study the reactivity of such functional groups as alkenes, carbonyl compounds, and aromatic compounds, as well as to investigate reactive intermediates, nucleophilic substitution, proton abstraction, pericyclic reactions, and photochemistry. The numerous structures are clear, appropriate, and useful for understanding the material, and the 100-plus challenging questions are similarly helpful. Extensive references; comprehensive index. A unique aspect is the inclusion of an interactive computer program to assist in performing simple H"uckel molecular orbital calculations. Upper-division undergraduate through professional. H. T. McKone; Saint Joseph College

Notas de autor provistas por Syndetics

Arvi Rauk, PhD, is Professor Emeritus in the Department of Chemistry at the University of Calgary in Calgary, Canada