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Full Description
Increase your understanding of molecular properties and reactions with this accessible textbook
The study of organic chemistry hinges on an understanding and capacity to predict molecular properties and reactions. Molecular Orbital Theory is a model grounded in quantum mechanics deployed by chemists to describe electron organization within a chemical structure. It unlocks some of the most prevalent reactions in organic chemistry.
Basic Concepts of Orbital Theory in Organic Chemistry provides a concise, accessible overview of this theory and its applications. Beginning with fundamental concepts such as the shape and relative energy of atomic orbitals, it proceeds to describe the way these orbitals combine to form molecular orbitals, with important ramifications for molecular properties. The result is a work which helps students and readers move beyond localized bonding models and achieve a greater understanding of organic chemical interactions.
In Basic Concepts of Orbital Theory in Organic Chemistry readers will also find:
Comprehensive explorations of stereoelectronic interactions and sigmatropic, cheletropic, and electrocyclic reactions,
Detailed discussions of hybrid orbitals, bond formation in atomic orbitals, the Hückel Molecular Orbital Method, and the conservation of molecular orbital symmetry
Sample exercises for organic chemistry students to help reinforce and retain essential concepts
Basic Concepts of Orbital Theory in Organic Chemistry is ideal for advanced undergraduate and graduate students in chemistry, particularly organic chemistry.
Contents
Preface ix
Chapter 1 Introduction and History of the Molecular Orbital Theory 1
Introduction 1
Nature of Electromagnetic Radiation 2
The Wave Nature of Light 3
Electromagnetic Spectrum 5
The Distinction Between Energy and Matter 6
The Particle Nature of Light 7
Mass and Momentum Associated with a Light Quantum 11
Wave-Particle Duality 13
Application of Quantum Mechanics to Atomic Structure 14
Schrödinger's Equation 19
Hydrogenic Orbitals 23
Why Doesn't the Electron Fall into the Nucleus? Bohr's Legacy and the Quantum Mechanical Model 32
Further Reading 33
Exercises 34
Chapter 2 Hybrid Orbitals 35
Introduction 35
Hybridisation Theory 37
Wavefunctions Associated with Hybrid Orbitals 42
Procedure to Build a Hybrid Orbital 43
Orthogonality of Wave Functions (Orbitals) 44
The Bent Bond or Tau Model 45
Effects of Hybridisation 45
Further Reading 51
Exercises 51
Chapter 3 Bond Formation from Atomic Orbitals 53
Introduction 53
Mixing of s Orbitals 53
Mixing of p Orbitals 58
Factors Affecting the Magnitude of Orbital Interactions 60
Bonding in Homo-Diatomic Molecules 62
Bonding in Hetero-Diatomic Molecules 68
Bonding in Triatomic Molecules 72
Conjugated Systems 84
Further Reading 84
Exercises 84
Chapter 4 The Hückel Molecular Orbital Method (HMO) 85
The Linear Combination of Atomic Orbitals (LCAO) Method 85
The Hückel Molecular Orbital (HMO) Method 86
Simplified Procedure for the Application of Hückel's Method 91
Application of Hückel's Method: Several Examples 92
Application to Larger Molecules 96
Scope and Limitations of the Hückel Molecular Orbital Method 97
Hückel Molecular Orbital Method in Cyclic π-Systems 97
Energy Diagrams for Acyclic Polyenes 101
π-Systems Containing Heteroatoms 102
Inclusion of Overlap Between Vicinal Atoms 106
The Shape of the Molecular Orbitals 108
Contribution of the AOs in a Molecular Orbital 108
Symmetry Simplifications in Alternant Hydrocarbons 112
Estimation of MO Energies and Coefficients 115
Bond Orders (P ij ) 116
Charge Distribution (q I ) 118
Index of Free Valence (f I ) 119
Further Reading 120
Exercises 121
Chapter 5 Interactions Between Molecular Orbitals: Chemical Reactions 123
Introduction 123
Molecular Orbital Theory of Selected Organic Reactions 127
Summary 140
Further Reading 141
Exercises 141
Chapter 6 Some Applications of Orbital Theory in Organic
Chemistry 143
Introduction 143
Ultraviolet Spectroscopy 143
Ionisation Potentials 146
Photoelectron Spectroscopy (PES) 147
Interactions Between π Orbitals 148
Interactions Between n-Orbitals 151
Electron Spectroscopy for Chemical Analysis (ESCA) Spectroscopy 155
Charge Transfer Complexes (EDA Complexes) 155
Further Reading 156
Exercises 157
Chapter 7 Conservation of Molecular Orbital
Symmetry: Introduction to Pericyclic
Reactions - Cycloaddition Reactions 159
Introduction 159
Concerted Reactions 160
Pericyclic Reactions 161
Principles of the Conservation of Orbital Symmetry 164
Symmetry Correlation Diagrams of Molecular Orbitals 164
Analysis of the Symmetry of the HOMO/LUMO Frontier Orbitals (FMO) 168
Analysis of the Nodal Properties at the Transition State of a Cyclisation Reaction 169
Cycloaddition Reactions 172
1,3-Butadiene + Ethylene ⇌ Cyclohexene 173
Two Ethylene Molecules ⇌ Cyclobutane 175
Supra- or Antarafacial Topicity in Cycloaddition Reactions 179
Effect of Secondary Interactions Between Molecular Orbitals 180
Further Reading 182
Exercises 182
Chapter 8 Cheletropic Reactions 185
Introduction 185
[2 + 2] Cheletropic Reactions 186
[4 + 2] Cheletropic Reactions 190
[6 + 2] Cheletropic Reactions 194
Further Reading 196
Exercises 196
Chapter 9 Electrocyclic Reactions 199
Introduction 199
1,3-Butadiene ⇋ Cyclobutene 201
1,3,5-Hexatriene ⇋ 1,3-Cyclohexadiene 204
Photochemical Electrocyclic Reactions 207
Further Reading 210
Exercises 210
Chapter 10 Sigmatropic Reactions 213
Introduction 213
[3,3] Sigmatropic Rearrangements 216
[1,3] Sigmatropic Rearrangements of Alkyl Groups 218
Analysis of Nodal Properties in the Transition State 221
[1,5] Sigmatropic Rearrangements of Alkyl Groups 221
[1,2] Sigmatropic Rearrangements of Alkyl Groups 225
[1,3] Sigmatropic Rearrangements of Hydrogen 227
[1,5] Sigmatropic Rearrangements of Hydrogen 228
Further Reading 231
Exercises 232
Chapter 11 1,3-Dipolar Cycloadditions 235
Introduction 235
Classification of 1,3-Dipolar Reactants 235
Frontier Molecular Orbital Analysis 236
Analysis of Nodal Properties in the Transition State 238
Types of 1,3-DPCA Reactions and Regioselectivity 239
1,3-DPCA Reactions with Diazoalkanes 242
1,3-DPCA Reactions with Nitrones 243
1,3-DPCA Reactions with Azomethine Ylides as the
1,3-Dipolar Reactant 245
1,3-DPCA Reactions with Nitrile Oxides as 1,3-Dipolar Reactants 247
1,3-DPCA Reactions with Azides, Osmium Tetroxide and
Ozone 248
Further Reading 251
Exercises 251
Chapter 12 Stereoelectronic Interactions 255
Introduction 255
Interpretation of the anomeric effect 258
Stereoelectronic interactions in S-C-P segments 261
Further Reading 266
Exercises 267
Index 269
