Modern Physical Organic Chemistry

Title Page......Page 1
Abbreviated Contents......Page 3
Contents......Page 5
Preface......Page 21
PART I  -  MOLECULAR STRUCTURE AND THERMODYNAMICS......Page 29
1  Introduction to Structure and Models of Bonding......Page 31
1.1.1 Quantum Numbers and Atomic Orbitals......Page 32
1.1.2 Electron Configurations and Electronic Diagrams......Page 33
1.1.4 Formal Charge......Page 34
1.1.5 VSEPR......Page 35
1.1.6 Hybridization......Page 36
1.1.7 A Hybrid Valence Bond/Molecular Orbital Model of Bonding......Page 38
1.1.8 Polar Covalent Bonding......Page 40
1.1.9 Bond Dipoles, Molecular Dipoles, and Quadrupoles......Page 45
1.1.10 Resonance......Page 48
1.1.11 Bond Lengths......Page 50
1.1.12 Polarizability......Page 52
1.2 A More Modern Theory of Organic Bonding......Page 54
1.2.1 Molecular Orbital Theory......Page 55
1.2.2 A Method for QMOT......Page 56
1.2.3 Methyl in Detail......Page 57
1.2.4 The CH2 Group in Detail......Page 61
1.3 Orbital Mixing-Building Larger Molecules......Page 63
1.3.1 Using Group Orbitals to Make Ethane......Page 64
1.3.2 Using Group Orbitals to Make Ethylene......Page 66
1.3.3 The Effects of Heteroatoms-Formaldehyde......Page 68
1.3.5 Three More Examples of Building Larger Molecules from Group Orbital......Page 71
1.3.6 Group Orbitals of Representative 'IT Systems: Benzene, Benzyl, and Allyl......Page 74
1.3.7 Understanding Common Functional Groups as Perturbations of Allyl......Page 77
1.3.8 The Three Center-Two Electron Bond......Page 78
1.3.9 Summary of the Concepts Involved in Our Second Model of Bonding......Page 79
1.4.1 Carbocations......Page 80
1.4.2 Carbanions......Page 84
1.4.3 Radicals......Page 85
1.4.4 Carbenes......Page 86
1.5 A Very Quick Look at Organometallic and Inorganic Bonding......Page 87
Summary and Outlook......Page 89
Exercises......Page 90
2  Strain and Stability......Page 93
2.1.1 The Concepts of Internal Strain and Relative Stability......Page 94
2.1.2 Types of Energy......Page 96
2.1.3 Bond Dissociation Energies......Page 98
2.1.4 An Introduction to Potential Functions and Surfaces-Bond Stretches......Page 101
2.1.5 Heats of Formation and Combustion......Page 105
2.1.6 The Group Increment Method......Page 107
2.2.1 Stability vs. Persistence......Page 110
2.2.2 Radicals......Page 111
2.2.3 Carbocations......Page 115
2.2.4 Carbanions......Page 119
2.3.1 Acyclic Systems-Torsional Potential Surfaces......Page 120
2.3.2 Basic Cyclic Systems......Page 128
2.4.1 Interactions Involving 'IT Systems......Page 140
2.4.2 Effects of Multiple Heteroatoms......Page 148
2.5.1 Long Bonds and Large Angles......Page 152
2.5.2 Small Rings......Page 153
2.5.3 Very Large Rotation Barriers......Page 155
2.6 Molecular Mechanics......Page 156
2.6.1 The Molecular Mechanics Model......Page 157
2.6.2 General Comments on the Molecular Mechanics Method......Page 161
2.6.3 Molecular Mechanics on Biomolecules and Unnatural Polymers-flModeling"......Page 163
2.6.4 Molecular Mechanics Studies of Reactions......Page 164
Summary and Outlook......Page 165
Exercises......Page 166
3.1 Solvent and Solution Properties......Page 173
3.1.2 Solvent Scales......Page 174
3.1.3 Solubility......Page 181
3.1.4 Solute Mobility......Page 183
3.1.5 The Thermodynamics of Solutions......Page 185
3.2 Binding Forces......Page 190
3.2.1 Ion Pairing Interactions......Page 191
3.2.2 Electrostatic Interactions Involving Dipoles......Page 193
3.2.3 Hydrogen Bonding......Page 196
3.2.4 nEffects......Page 208
3.2.5 Induced-Dipole Interactions......Page 214
3.2.6 The Hydrophobic Effect......Page 217
3.3 Computational Modeling of Solvation......Page 222
3.3.1 Continuum Solvation Models......Page 224
3.3.2 Explicit Solvation Models......Page 225
3.3.3 Monte Carlo (MC) Methods......Page 226
3.3.4 Molecular Dynamics (MD)......Page 227
3.3.5 Statistical Perturbation Theory/Free Energy Perturbation......Page 228
Summary and Outlook......Page 229
Exercises......Page 230
4.1 Thermodynamic Analyses of Binding Phenomena......Page 235
4.1.1 General Thermodynamics of Binding......Page 236
4.1.2 The Binding Isotherm......Page 244
4.1.3 Experimental Methods......Page 247
4.2 Molecular Recognition......Page 250
4.2.1 Complementarity and Preorganization......Page 252
4.2.2 Molecular Recognition with a Large Ion Pairing Component......Page 256
4.3 Supramolecular Chemistry......Page 271
Exercises......Page 281
5.1 Bronsted Acid-Base Chemistry......Page 287
5.2.1 pKa......Page 289
5.2.2 pH......Page 290
5.2.3 The Leveling Effect......Page 292
5.2.5 Acidity Functions: Acidity Scales for Highly Concentrated Acidic Solutions......Page 294
5.2.6 Super Acids......Page 298
5.3 Nonaqueous Systems......Page 299
5.3.2 Solution Phase vs. Gas Phase......Page 301
5.4.1 Methods Used to Measure Weak Acid Strength......Page 304
5.4.2 Two Guiding Principles for Predicting Relative Acidities......Page 305
5.4.4 Resonance......Page 306
5.4.7 Hybridization......Page 311
5.4.9 Solvation......Page 312
5.5 Acids and Bases of Biological Interest......Page 313
5.6 Lewis Acids/Bases and Electrophiles/Nucleophiles......Page 316
5.6.1 The Concept of Hard and Soft Acids and Bases, General Lessons for Lewis Acid-Base Interactions, and Relative Nudeophilicity......Page 317
Exercises......Page 320
6.1 Stereogenicityand Stereoisomerism......Page 325
6.1.1 Basic Concepts and Terminology......Page 326
6.1.2 Stereochemical Descriptors......Page 331
6.1.3 Distinguishing Enantiomers......Page 334
6.2.2 Chirality and Symmetry......Page 339
6.2.3 Symmetry Arguments......Page 341
6.2.4 Focusing on Carbon......Page 342
6.3.1 Homotopic, Enantiotopic, and Diastereotopic......Page 343
6.3.2 Topicity Descriptors-Pro-RI Pro-S and Re/Si......Page 344
6.4.1 Simple Guidelines for Reaction Stereochemistry......Page 345
6.4.2 Stereospecific and Stereoselective Reactions......Page 347
6.5 Symmetry and Time Scale......Page 350
6.6 Topological and Supramolecular Stereochemistry......Page 352
6.6.1 Loops and Knots......Page 353
6.6.3 Nonplanar Graphs......Page 354
6.6.4 Achievements in Topological and Supramolecular Stereochemistry......Page 355
6.7 Stereochemical Issues in Polymer Chemistry......Page 359
6.8.1 The Linkages of Proteins, Nucleic Acids, and Polysaccharides......Page 361
6.8.2 Helicity......Page 364
6.8.3 The Origin of Chirality in Nature......Page 367
6.9 Stereochemical Terminology......Page 368
Exercises......Page 372
PART II  -  REACTIVITY, KINETICS, AND MECHANISMS......Page 381
7  Energy Surfaces and Kinetic Analyses......Page 383
7.1 Energy Surfaces and Related Concepts......Page 384
7.1.1 Energy Surfaces......Page 385
7.1.2 Reaction Coordinate Diagrams......Page 387
7.1.3 What is the Nature of the Activated Complex/Transition State?......Page 390
7.1.4 Rates and Rate Constants......Page 391
7.1.5 Reaction Order and Rate Laws......Page 392
7.2.1 The Mathematics of Transition State Theory......Page 393
7.2.2 Relationship to the Arrhenius Rate Law......Page 395
7.2.3 Boltzmann Distributions and Temperature Dependence......Page 396
7.2.4 Revisiting "What is the Nature of the Activated Complex?" and Why Does TST Work?......Page 397
7.2.5 Experimental Determinations of Activation Parameters and Arrhenius Parameters......Page 398
7.2.7 Is TST Completely Correct? The Dynamic Behavior of Organic Reactive Intermediates......Page 400
7.3.1 The Hammond Postulate......Page 402
7.3.2 The Reactivity vs. Selectivity Principle......Page 405
7.3.3 The Curtin-Hammett Principle......Page 406
7.3.4 Microscopic Reversibility......Page 407
7.3.5 Kinetic vs. Thermodynamic Control......Page 408
7.4.1 How Kinetic Experiments are Performed......Page 410
7.4.2 Kinetic Analyses for Simple Mechanisms......Page 412
7.5.1 Steady State Kinetics......Page 418
7.5.2 Using the SSA to Predict Changes in Kinetic Order......Page 423
7.5.3 Saturation Kinetics......Page 424
7.6 Methods for Following Kinetics......Page 425
7.6.2 Fast Kinetics Techniques......Page 426
7.6.3 Relaxation Methods......Page 429
7.6.4 Summary of Kinetic Analyses......Page 430
7.7.1 Marcus Theory......Page 431
7.7.2 Marcus Theory Applied to Electron Transfer......Page 433
7.8.1 Variation in Transition State Structures Across a Series of Related Reactions-An Example Using Substitution Reactions......Page 435
7.8.2 More O'Ferrall-Jencks Plots......Page 437
7.8.3 Changes in Vibrational State Along the Reaction Coordinate­Relating the Third Coordinate to Entropy......Page 440
Exercises......Page 441
8.1 Isotope Effects......Page 449
8.1.2 The Origin of Primary Kinetic Isotope Effects......Page 450
8.1.3 The Origin of Secondary Kinetic Isotope Effects......Page 456
8.1.4 Equilibrium Isotope Effects......Page 460
8.1.5 Tunneling......Page 463
8.1.6 Solvent Isotope Effects......Page 465
8.2 Substituent Effects......Page 469
8.2.1 The Origin of Substituent Effects......Page 471
8.3.1 Sigma (0")......Page 473
8.3.2 Rho (p)......Page 475
8.3.3 The Power of Hammett Plots for Deciphering Mechanisms......Page 476
8.3.4 Deviations from Linearity......Page 477
8.3.5 Separating Resonance from Induction......Page 479
8.4.1 Steric and Polar Effects-Taft Parameters......Page 482
8.4.2 Solvent Effects-Grunwald-Winstein Plots......Page 483
8.4.3 Schleyer Adaptation......Page 485
8.4.4 Nucleophilicity and Nucleofugality......Page 486
8.4.5 Swain-Scott Parameters-Nucleophilicity Parameters......Page 489
8.4.6 Edwards and Ritchie Correlations......Page 491
8.5.2 BLG......Page 492
8.6 Why do Linear Free Energy Relationships Work?......Page 494
8.6.1 General Mathematics of LFERs......Page 495
8.6.2 Conditions to Create an LFER......Page 496
8.6.4 Why does Enthalpy-Entropy Compensation Occur?......Page 497
8.7 Summary of Linear Free Energy Relationships......Page 498
8.8 Miscellaneous Experiments for Studying Mechanisms......Page 499
8.8.1 Product Identification......Page 500
8.8.2 Changing the Reactant Structure to Divert or Trap a Proposed Intermediate......Page 501
8.8.3 Trapping and Competition Experiments......Page 502
8.8.4 Checking for a Common Intermediate......Page 503
8.8.6 Stereochemical Analysis......Page 504
8.8.7 Isotope Scrambling......Page 505
8.8.8 Techniques to Study Radicals: Clocks and Traps......Page 506
8.8.10 Transient Spectroscopy......Page 508
8.8.11 Stable Media......Page 509
Exercises......Page 510
9  Catalysis......Page 517
9.1 General Principles of Catalysis......Page 518
9.1.1 Binding the Transition State Better than the Ground State......Page 519
9.1.2 A Thermodynamic Cycle Analysis......Page 521
9.1.3 A Spatial Temporal Approach......Page 522
9.2.2 Proximity as a Binding Phenomenon......Page 523
9.2.3 Electrophilic Catalysis......Page 527
9.2.5 Nucleophilic Catalysis......Page 530
9.2.6 Covalent Catalysis......Page 532
9.2.7 Strain and Distortion......Page 533
9.3.1 Specific Catalysis......Page 535
9.3.2 General Catalysis......Page 538
9.3.3 A Kinetic Equivalency......Page 542
9.3.4 Concerted or Sequential General-Acid-General-Base Catalysis......Page 543
9.3.5 The Bronsted Catalysis Law and Its Ramifications......Page 544
9.3.6 Predicting General-Acid or General-Base Catalysis......Page 548
9.3.7 The Dynamics of Proton Transfers......Page 550
9.4.1 Michaelis-Menten Kinetics......Page 551
9.4.2 The Meaning of KMI kcatl and kca/KM......Page 552
9.4.3 Enzyme Active Sites......Page 553
9.4.4 [S] vs. KM-Reaction Coordinate Diagrams......Page 555
9.4.5 Supramolecular Interactions......Page 557
Summary and Outlook......Page 558
Exercises......Page 559
10  Organic Reaction Mechanisms, Part 1: Reactions Involving Additions and / or Eliminations......Page 565
10.1 Predicting Organic Reactivity......Page 566
10.1.1 A Useful Paradigm for Polar Reactions......Page 567
10.1.3 In Preparation for the Following Sections......Page 569
10.2 Hydration of Carbonyl Structures......Page 570
10.2.1 Acid-Base Catalysis......Page 571
10.2.2 The Thermodynamics of the Formation of Geminal Diols and Hemiacetals......Page 572
10.3 Electrophilic Addition of Water to Alkenes and Alkynes: Hydration......Page 573
10.3.3 Regiochemistry......Page 574
10.3.4 Alkyne Hydration......Page 575
10.4.2 Experimental Observations Related to Regiochemistry and Stereochemistry......Page 576
10.5.1 Electron Pushing......Page 579
10.5.3 Other Evidence Supporting a G Complex......Page 580
10.5.4 Mechanistic Variants......Page 581
10.6 Hydroboration......Page 582
10.7 Epoxidation......Page 583
10.8 Nucleophilic Additions to Carbonyl Compounds......Page 584
10.8.1 Electron Pushing for a Few Nucleophilic Additions......Page 585
10.8.2 Experimental Observations for Cyanohydrin Formation......Page 587
10.8.3 Experimental Observations for Grignard Reactions......Page 588
10.8.5 Orbital Considerations......Page 589
10.8.6 Conformational Effects in Additions to Carbonyl Compounds......Page 590
10.8.7 Stereochemistry of Nucleophilic Additions......Page 591
10.9.3 Regiochemistry of Addition......Page 595
10.9.4 Baldwin's Rules......Page 596
10.10.1 Electron Pushing for Radical Additions......Page 597
10.10.2 Radical Initiators......Page 598
10.10.4 Termination......Page 599
10.11 Carbene Additions and Insertions......Page 600
10.11.2 Carbene Generation......Page 602
10.11.3 Experimental Observations for Carbene Reactions......Page 603
Eliminations......Page 604
10.12.2 Stereochemical and Isotope Labeling Evidence......Page 605
10.12.3 Catalysis of the Hydrolysis of Acetals......Page 606
10.12.4 Stereoelectronic Effects......Page 607
10.12.5 CrO3 Oxidation-The Jones Reagent......Page 608
10.13.1 Electron Pushing and Definitions......Page 609
10.13.2 Some Experimental Observations for E2 and E1 Reactions......Page 610
10.13.3 Contrasting Elimination and Substitution......Page 611
10.13.5 Kinetics and Experimental Observations for E1cB......Page 612
10.13.6 Contrasting E2, E1, and E1cB......Page 614
10.13.7 Regiochemistry of Eliminations......Page 616
10.13.8 Stereochemistry of Eliminations-Orbital Considerations......Page 618
10.13.9 Dehydration......Page 620
10.13.10 Thermal Eliminations......Page 622
Combining Addition and Elimination Reactions (Substitutions at sp2 Centers)......Page 624
10.15 The Addition of Nitrogen Nucleophiles to Carbonyl Structures, Followed by Elimination......Page 625
10.15.2 Acid-Base Catalysis......Page 626
10.16 The Addition of Carbon Nucleophiles, Followed by Elimination-The Wittig Reaction......Page 627
10.17.1 General Electron-Pushing Schemes......Page 628
10.17.2 Isotope Scrambling......Page 629
10.17.3 Predicting the Site of Cleavage for Acyl Transfers from Esters......Page 630
10.18.1 Electron Pushing for Electrophilic Aromatic Substitutions......Page 635
10.18.3 Intermediate Complexes......Page 636
10.18.4 Regiochemistry and Relative Rates of Aromatic Substitution......Page 637
10.19.2 Experimental Observations......Page 639
10.20.1 Electron Pushing for Benzyne Reactions......Page 640
10.20.3 Substituent Effects......Page 641
10.22.1 Electron Pushing......Page 643
10.22.3 Regiochemistry......Page 644
Exercises......Page 645
Substitution a to a Carbonyl Center: Enol and Enolate Chemistry......Page 655
11.1.2 The Thermodynamics of Enol Formation......Page 656
11.1.4 Kinetic vs. Thermodynamic Control in Enolate and Enol Formation......Page 657
11.2.2 A Few Experimental Observations......Page 659
11.3.1 Electron Pushing......Page 660
11.3.2 Stereochemistry: Conformational Effects......Page 661
11.4.2 Conformational Effects on the Aldol Reaction......Page 662
11.5.1 SN2 and SN1 Electron-Pushing Examples......Page 665
11.5.2 Kinetics......Page 666
11.5.3 Competition Experiments and Product Analyses......Page 667
11.5.4 Stereochemistry......Page 668
11.5.6 Solvent Effects......Page 671
11.5.8 An Overall Picture of SN2 and SNI Reactions......Page 674
11.5.9 Structure-Function Correlations with the Nucleophile......Page 676
11.5.11 Structure-Function Correlations with the R Group......Page 679
11.5.12 Carbocation Rearrangements......Page 684
11.5.13 Anchimeric Assistance in SN1 Reactions......Page 687
11.5.14 SN1 Reactions Involving Non-Classical Carbocations......Page 689
11.5.16 The Interplay Between Substitution and Elimination......Page 695
11.6.1 The SET Reaction-Electron Pushing......Page 696
11.6.3 Radical Rearrangements as Evidence......Page 697
11.6.5 The SRNI Reaction-Electron Pushing......Page 698
11.7.3 Regiochemistry of Free Radical Halogenation......Page 699
11.7.4 Autoxidation: Addition of O2 into C-H Bonds......Page 701
11.8 Migrations to Electrophilic Carbons......Page 702
11.8.3 Migratory Aptitudes in the Pinacol Rearrangement......Page 703
11.8.4 Stereoelectronic and Stereochemical Considerations in the Pinacol Rearrangement......Page 704
11.9.1 Electron Pushing in the Beckmann Rearrangement......Page 706
11.9.2 Electron Pushing for the Hofmann Rearrangement......Page 707
11.9.5 A Few Experimental Observations for the Beckmann Rearrangement......Page 708
11.9.7 A Few Experimental Observations for the Baeyer-Villiger Oxidation......Page 709
11.10.1 Electron Pushing......Page 710
11.11.1 Hydrogen Shifts......Page 711
11.11.2 Aryl and Vinyl Shifts......Page 712
11.12 Rearrangements and Isomerizations Involving Biradicals......Page 713
11.12.1 Electron Pushing Involving Biradicals......Page 714
11.12.2 Tetramethylene......Page 715
11.12.3 Trimethylene......Page 717
11.12.4 Trimethylenemethane......Page 721
Exercises......Page 723
12.1 The Basics of Organometallic Complexes......Page 733
12.1.1 Electron Counting and Oxidation State......Page 734
12.1.3 Standard Geometries......Page 738
12.1.5 Electron Pushing with Organometallic Structures......Page 739
12.1.6 d Orbital Splitting Patterns......Page 740
12.1.7 Stabilizing Reactive Ligands......Page 741
12.2.1 Ligand Exchange Reactions......Page 742
12.2.2 Oxidative Addition......Page 745
12.2.3 Reductive Elimination......Page 752
12.2.4 a- and B-Eliminations......Page 755
12.2.5 Migratory Insertions......Page 757
12.2.6 Electrophilic Addition to Ligands......Page 761
12.2.7 Nucleophilic Addition to Ligands......Page 762
12.3 Combining the Individual Reactions into  Overall Transformations and Cycles......Page 765
12.3.2 The Monsanto Acetic Acid Synthesis......Page 766
12.3.3 Hydroformylation......Page 767
12.3.4 The Water-Gas Shift Reaction......Page 768
12.3.5 Olefin Oxidation-The Wacker Process......Page 769
12.3.6 Palladium Coupling Reactions......Page 770
12.3.7 Allylic Alkylation......Page 771
12.3.8 Olefin Metathesis......Page 772
Summary and Outlook......Page 775
Exercises......Page 776
13  Organic Polymer and Materials Chemistry......Page 781
13.1.1 Molecular Weight Analysis of Polymers......Page 782
13.1.2 Thermal Transitions-Thermoplastics and Elastomers......Page 785
13.1.3 Basic Polymer Topologies......Page 787
13.1.4 Polymer-Polymer Phase Behavior......Page 788
13.1.5 Polymer Processing......Page 790
13.1.6 Novel Topologies-Dendrimers and Hyperbranched Polymers......Page 791
13.1.7 Liquid Crystals......Page 797
13.1.8 Fullerenes and Carbon Nanotubes......Page 803
13.2.1 General Issues......Page 807
13.2.2 Polymerization Kinetics......Page 810
13.2.3 Condensation Polymerization......Page 816
13.2.4 Radical Polymerization......Page 819
13.2.5 Anionic Polymerization......Page 821
13.2.7 Ziegler-Natta and Related Polymerizations......Page 822
13.2.8 Ring-Opening Polymerization......Page 825
13.2.9 Group Transfer Polymerization (GTP)......Page 827
Summary and Outlook......Page 828
Exercises......Page 829
PART III  -  ELECTRONIC STRUCTURE: THEORY AND APPLICATIONS......Page 833
14  Advanced Concepts in Electronic Structure Theory......Page 835
14.1.1 The Nature of Wavefunctions......Page 836
14.1.3 The Hamiltonian......Page 837
14.1.4 The Nature of the......Page 0
14.1.5 Why do Bonds Form?......Page 840
14.2.1 Ab Initio Molecular Orbital Theory......Page 843
14.2.2 Secular Determinants-A Bridge Between Ab Initio, Semi-Empirical/ Approximate, and Perturbational Molecular Orbital Theory......Page 856
14.2.3 Semi-Empirical and Approximate Methods......Page 861
14.2.4 Some General Comments on Computational Quantum Mechanics......Page 863
14.2.5 An Alternative: Density Functional Theory (OFT)......Page 864
14.3 A Brief Overview of the Implementation and Results of HMOT......Page 865
14.3.1 Implementing Hiickel Theory......Page 866
14.3.2 HMOT of Cyclic Pi Systems......Page 868
14.3.3 HMOT of Linear Pi Systems......Page 869
14.3.4 Alternant Hydrocarbons......Page 870
14.4 Perturbation Theory-Orbital Mixing Rules......Page 872
14.4.2 Mixing of Non-Degenerate Orbitals-Second-Order Perturbations......Page 873
14.5.1 Arenes: Aromaticity and Antiaromaticity......Page 874
14.5.2 Cyclopropane and Cyclopropylcarbinyl-Walsh Orbitals......Page 876
14.5.3 Planar Methane......Page 881
14.5.4 Through-Bond Coupling......Page 882
14.5.5 Unique Bonding Capabilities of Carbocations­-Non-Classical Ions and Hypervalent Carbon......Page 883
14.5.6 Spin Preferences......Page 887
14.6 Organometallic Complexes......Page 890
14.6.1 Group Orbitals for Metals......Page 891
14.6.2 The Isolobal Analogy......Page 894
14.6.3 Using the Group Orbitals to Construct Organometallic Complexes......Page 895
Exercises......Page 896
15  Thermal Pericyclic Reactions......Page 905
15.2 A Detailed Analysis of Two Simple Cycloadditions......Page 906
15.2.1 Orbital Symmetry Diagrams......Page 907
15.2.2 State Correlation Diagrams......Page 911
15.2.3 Frontier Molecular Orbital (FMO) Theory......Page 916
15.2.4 Aromatic Transition State Theory/Topology......Page 917
15.2.5 The Generalized Orbital Symmetry Rule......Page 918
15.2.7 Photochemical Peri cyclic Reactions......Page 920
15.3 Cycloadditions......Page 921
15.3.1 An Allowed Geometry for [2+2] Cycloadditions......Page 922
15.3.3 General Experimental Observations......Page 923
15.3.4 Stereochemistry and Regiochemistry of the Diels-Alder Reaction......Page 924
15.3.6 Experimental Observations for 1,3-Dipolar Cycloadditions......Page 929
15.3.7 Retrocycloadditions......Page 930
15.4.1 Terminology......Page 931
15.4.2 Theoretical Analyses......Page 932
15.4.3 Experimental Observations: Stereochemistry......Page 934
15.4.4 Torquoselectivity......Page 936
15.5 Sigmatropic Rearrangements......Page 938
15.5.1 Theory......Page 939
15.5.2 Experimental Observations: A Focus on Stereochemistry......Page 941
15.5.3 The Mechanism of the Cope Rearrangement......Page 944
15.5.4 The Claisen Rearrangement......Page 949
15.6 Cheletropic Reactions......Page 952
15.6.1 Theoretical Analyses......Page 954
15.6.2 Carbene Additions......Page 955
Summary and Outlook......Page 956
Exercises......Page 957
16  Photochemistry......Page 963
16.1.1 Electromagnetic Radiation......Page 964
16.1.2 Absorption......Page 967
16.1.3 Radiationless Vibrational Relaxation......Page 972
16.1.4 Fluorescence......Page 973
16.1.5 Internal Conversion (IC)......Page 977
16.1.6 Intersystem Crossing (ISC)......Page 978
16.1.7 Phosphorescence......Page 979
16.1.9 Summary of Photophysical Processes......Page 980
16.2.2 Quenching, Excimers, and Exciplexes......Page 981
16.2.3 Energy Transfer I. The Dexter Mechanism-Sensitization......Page 984
16.2.4 Energy Transfer II. The Forster Mechanism......Page 986
16.2.5 FRET......Page 988
16.3.1 Theoretical Considerations-Funnels......Page 990
16.3.3 Olefin Isomerization......Page 993
16.3.4 Reversal of Pericyclic Selection Rules......Page 996
16.3.5 Photocycloaddition Reactions......Page 998
16.3.6 The Di-Pi-Methane Rearrangement......Page 1002
16.3.7 Carbonyls Part I: The Norrish I Reaction......Page 1004
16.3.8 Carbonyls Part II: Photoreduction and the Norrish II Reaction......Page 1006
16.3.9 Nitrobenzyl Photochemistry: JlCaged" Compounds......Page 1008
16.3.10 Elimination of N2: Azo Compounds, Diazo Compounds, Diazirines, and Azides......Page 1009
16.4.1 Potential Energy Surface for a Chemiluminescent Reaction......Page 1013
16.4.2 Typical Chemiluminescent Reactions......Page 1014
16.4.3 Dioxetane Thermolysis......Page 1015
16.5 Singlet Oxygen......Page 1017
Exercises......Page 1021
17.1 Theory......Page 1029
17.1.1 Infinite Pi Systems--An Introduction to Band Structures......Page 1030
17.1.2 The Peierls Distortion......Page 1037
17.1.3 Doping......Page 1039
17.2.1 Conductivity......Page 1044
17.2.2 Polyacetylene......Page 1045
17.2.3 Polyarenes and Polyarenevinylenes......Page 1046
17.2.4 Polyaniline......Page 1049
17.3 Organic Magnetic Materials......Page 1050
17.3.1 Magnetism......Page 1051
17.3.2 The Molecular Approach to Organic Magnetic Materials......Page 1052
17.3.3 The Polymer Approach to Organic Magnetic Materials­-Very High-Spin Organic Molecules......Page 1055
17.4 Superconductivity......Page 1058
17.4.1 Organic Metals/Synthetic Metals......Page 1060
17.5 Non-Linear Optics (NLO)......Page 1061
17.6.1 Photolithography......Page 1064
17.6.2 Negative Photoresists......Page 1065
17.6.3 Positive Photoresists......Page 1066
Summary and Outlook......Page 1069
Exercises......Page 1070
1  Conversion Factors and Other Useful Data......Page 1075
2  Electrostatic Potential Surfaces for Representative Organic Molecules......Page 1077
3  Group Orbitals of Common Functional Groups: Representative Examples Using Simple Molecules......Page 1079
4  The Organic Structures of Biology......Page 1085
A5.1 The Rudiments of Pushing Electrons......Page 1089
A5.2 Electron Sources and Sinks for Two-Electron Flow......Page 1090
A5.3 How to Denote Resonance......Page 1092
A5.4 Common Electron-Pushing Errors......Page 1093
A5.5 Complex Reactions-Drawing a Chemically Reasonable Mechanism......Page 1096
A5.6 Two Case Studies of Predicting Reaction Mechanisms......Page 1097
A5.7 Pushing Electrons for Radical Reactions......Page 1099
Practice Problems for Pushing Electrons......Page 1101
Reaction Mechanism Nomenclature......Page 1103
Index......Page 1107