High Resolution NMR

PrefaceAcknowledgments1. Introduction 1.1 Historical 1.2 High Resolution NMR References2. The Theory of NMR 2.1 Nuclear Spin and Magnetic Moment 2.2 Classical Mechanical Description of NMR 2.3 Quantum Mechanical Description of NMR 2.4 Effect of the Boltzmann Distribution 2.5 Spin-Lattice Relaxation 2.6 Line Widths 2.7 Saturation 2.8 The Bloch Equations; Nuclear Induction 2.9 Ringing References Problems3. Instrumentation and Techniques 3.1 Basic NMR Apparatus 3.2 Requirements for High Resolution NMR 3.3 Modulation and Phase Detection 3.4 Field/Frequency Control 3.5 Signal/Noise and Size of Sample 3.6 Superconducting Magnets 3.7 Intensity Measurements 3.8 References 3.9 Magnetic Susceptibility Measurements 3.10 Frequency Calibration 3.11 Control of Sample Temperature 3.12 Useful Solvents 3.13 Sampling Techniques 3.14 Micro Techniques 3.15 Adiabatic Rapid Passage 3.16 Pulse Techniques 3.17 Double Resonance Techniques References Problems4. Chemical Shifts 4.1 The Origin of Chemical Shifts 4.2 Reference Compounds 4.3 Chemical Shift Scales 4.4 Magnetic Susceptibility Correction 4.5 Empirical Correlations of Chemical Shifts 4.6 Theory of Chemical Shifts 4.7 Effect of Electron Density 4.8 Magnetic Anisotropy and Chemical Shifts 4.9 Ring Currents 4.10 Paramagnetic Species 4.11 Nuclei Other than Hydrogen 4.12 Tabulations of Chemical Shifts and Spectra 4.13 Empirical Estimation of Chemical Shifts References Problems5. Electron-Coupled Spin-Spin Interactions 5.1 Origin of Spin-Spin Coupling 5.2 Coupling between Groups of Equivalent Nuclei 5.3 First-Order Analysis 5.4 Signs of Coupling Constants 5.5 Theory of Spin-Spin Coupling 5.6 Some Observed Coupling Constants 5.7 Correlation of Coupling Constants with Other Physical Properties References Problems6. The Use of NMR in Structure Elucidation 6.1 A Systematic Approach to the Interpretation of NMR Spectra 6.2 Spectra of Polymers in Solution References Problems7. Analysis of Complex Spectra 7.1 Notation 7.2 Energy Levels and Transitions in an AX System 7.3 Quantum Mechanical Formalism 7.4 Nuclear Spin Basis Functions 7.5 The Spin Hamiltonian 7.6 The Two-Spin System without Coupling 7.7 Factoring the Secular Equation 7.8 Two Coupled Spins 7.9 Selection Rules and Intensities 7.10 The AB Spectrum 7.11 Spectral Contributions from Equivalent Nuclei 7.12 Symmetry of Wave Functions 7.13 Summary of Rules for Calculating Spectra 7.14 The Three-Spin System: ABC 7.15 The A2B System 7.16 The A3B System; Subspectral Analysis 7.17 The ABX System 7.18 Analysis of an ABX Spectrum 7.19 Relative Signs of JAX and JBX in an ABX Spectrum 7.20 ABX Patterns; Deceptively Simple Spectra 7.21 "Virtual Coupling" 7.22 The AA'BB' and AA'XX' Systems 7.23 Other Complex Spectra 7.24 Aids in the Analysis of Complex Spectra 7.25 Use of Liquid Crystals as Solvents References Problems8. Theory and Application of Double Resonance 8.1 Notation and Terminology 8.2 Experimental Techniques 8.3 Theory of Double Resonance 8.4 Structure Elucidation 8.5 Location of "Hidden" Lines 8.6 Determination of Chemical Shifts 8.7 Relative Signs of Coupling Constants 8.8 Determination of Energy Level Arrangements 8.9 Other Applications References Problems9. Relaxation 9.1 Processes for Spin-Lattice Relaxation 9.2 Nuclear Magnetic Dipole Interactions 9.3 The Effect of Anisotropic Shielding 9.4 Electric Quadrupole Relaxation 9.5 Relaxation by Paramagnetic Substances 9.6 Chemical Applications 9.7 Measurement of Relaxation Times References Problems10. Effects of Exchange Processes 10.1 Spectra of Exchanging Systems 10.2 Theory of Chemical Exchange 10.3 Collapse of Spin Multiplets 10.4 More Complete Theories of Exchange 10.5 Double Resonance and Pulse Techniques 10.6 Asymmetry and Internal Rotation References Problems11. Solvent Effects and Hydrogen Bonding 11.1 Medium Effects on Chemical Shifts 11.2 Solvent Effects on Coupling Constants 11.3 Solvent Effects on Relaxation and Exchange Rates 11.4 Hydrogen Bonding References12. Use of NMR in Quantitative Analysis 12.1 Advantages of NMR in Quantitative Analysis 12.2 Drawbacks and Problems in the Use of NMR in Quantitative Analysis 12.3 Some Analytical Uses of NMR ReferencesAppendix A Nuclear Spins, Magnetic Moments, Resonance FrequenciesAppendix B Proton NMR Spectra of "Unknowns"Appendix C General NMR ReferencesAppendix D Answers to Selected ProblemsSubject Index