Multinuclear NMR

ISBN-13: 9781461289999 / Angielski / Miękka / 2011 / 660 str.

J. Mason

Opis

With the power and range of modern pulse spectrometers the compass of NMR spec troscopy is now very large for a single book-but we have undertaken this. Our book covers the Periodic Table as multinuclear spectrometers do, and introductory chapters are devoted to the essentials of the NMR experiment and its products. Primary products are chemical shifts (including anisotropies), spin-spin coupling constants, and relaxation times; the ultimate product is a knowledge of content and constitution, dynamic as well as static. Our province is chemical and biochemical rather than physical or technical; only passing reference is made to metallic solids or unstable species, or to practical NMR spectroscopy. Our aim is depth as well as breadth, to explain the fundamental processes, whether of nuclear magnetic shielding, spin-spin coupling, relaxation, or the multiple pulse sequences that have allowed the development of high-resolution studies of solids, multidimensional NMR spectroscopy, techniques for sensitivity enhancement, and so on. This book therefore combines the functions of advanced textbook and reference book. For reasonably comprehensive coverage in a single volume we have sum marized the information in tables and charts, and included all leading references."

Spis treści

1 Introduction.- 2 The Parameters of NMR Spectroscopy.- 1. Nuclear Properties of the Elements and the Resonance Condition.- 2. The Nucleus in a Chemical Environment.- 2.1. The Chemical Shift and the Shielding Tensor.- 2.2. Dipolar (D) Coupling.- 2.3. Indirect Spin-Spin (J) Coupling.- 2.4. Electric Quadrupole Coupling.- 2.5. Relaxation.- 3. The Larmor Precession and the Bloch Equations.- 4. The Fourier Transform Technique.- 5. Multipulse and Multiple Resonance Techniques.- 5.1. Double Resonance Experiments.- 5.2. Techniques for Signal Enhancement.- 5.3. Techniques in Aid of Spectral Analysis and Assignment.- 6. Oriented Systems.- 6.1. High Resolution NMR Techniques for Solids.- 6.2. Experimental Determination of Tensor Components of ?, J, D, and q.- 7. The NMR Time Scale.- 8. Physical Effects on the NMR Parameters.- 8.1. Medium and Temperature Effects.- 8.2. Isotope Effects.- 8.3. Effects of Paramagnetic Substances.- References.- 3 The Chemical Shift.- 1. Nuclear Magnetic Shielding and the Chemical Shift.- 1.1 The Absolute Shielding Tensor.- 1.2. The Diamagnetic and Paramagnetic Contributions to Shielding.- 1.3. The Relationship between ?p and the Nuclear Spin-Rotation Constant.- 1.4. Molecular Symmetry and Nuclear Magnetic Shielding.- 1.5. Absolute Shielding Scales.- 1.6. Experimental Methods of Determining the Shielding Anisotropy.- 2. Theoretical Description.- 2.1. Computational Schemes.- 2.2. Relativistic Effects.- 2.3. Approximate Calculations and Models.- 3. Patterns of Chemical Shifts.- 3.1. Chemical Shift Ranges of the Nuclei.- 3.2. Scaling of Chemical Shifts.- 3.3. General Factors in the Shielding of Main-Group and Transition Metal Nuclei.- 3.4. Dependence of Nuclear Shielding on Charge Density, Oxidation State, and Substituent Electronegativity.- 3.5. Correlations with Electronic Excitation and Ionization Energies.- 3.6. Substituent Effects.- 4. Correlations of Chemical Shifts with Other Molecular Properties.- 4.1. Nuclear Quadrupole Coupling Constants.- 4.2. Van Vleck Paramagnetism, and the Electronic g Tensor.- 4.3. Spin-Spin Coupling Constants and Relaxation Times.- 4.4. Bond Properties.- 5. Shifts in Paramagnetic Systems.- 6. Effects of Intermolecular Interactions and Intramolecular Dynamics.- 6.1. Medium Effects.- 6.2. Rovibrational Averaging and Isotope Effects.- 6.3. Dynamic Processes: Fluxional, Conformational and Exchange Equilibria.- References.- 4 Spin-Spin Coupling.- 1. General Considerations.- 1.1. Mechanisms of Spin-Spin Coupling.- 1.2. Anisotropy of the Spin-Spin Coupling.- 1.3. Methods of Determining Signs of Coupling Constants.- 2. Empirical Patterns of Coupling Constants.- 2.1. Signs and General Magnitudes of nK:(XY).- 2.2. Structural Factors Affecting 1K.- 2.3. Structural Factors Affecting the Sign and Magnitude of 2K.- 2.4. Structural Factors Affecting the Sign and Magnitude of 3K.- 3. Effects of Intermolecular Interactions and Intramolecular Dynamics on Spin-Spin Coupling.- 3.1. Averaging via Rotameric Equilibria and Intramolecular Rearrangement.- 3.2. Isotope Effects.- 3.3. Chemical Exchange and Medium Effects.- 4. Theoretical Description.- 4.1. Computational Schemes.- 4.2. Relative Importance of the Fermi Contact, Spin Dipolar and Orbital Terms.- 4.3. Relativistic Effects.- 4.4. Approximate Calculations and Models.- References.- 5 Relaxation and Related Time-Dependent Processes.- 1. Importance.- 2. Definitions.- 2.1. Macroscopic Definition of T1 and T2: Bloch Equations.- 2.2. Microscopic Interpretation.- 2.3. Nuclear Overhauser Enhancement.- 2.4. Relaxation in the Rotating Frame: T1?.- 3. Microscopic Theory.- 3.1. Spin-Lattice Relaxation.- 3.2. Spin-Spin Relaxation.- 3.3. Dependence of Spectral Density upon Frequency.- 3.4. The Static Part V.- 3.5. More Complete Treatments.- 4. Specific Mechanisms.- 4.1. Dipole-Dipole Relaxation.- 4.2. Scalar Interactions.- 4.3. Shielding Anisotropy.- 4.4. Spin-Rotation Interactions.- 4.5. Electric Quadrupole Interactions.- 5. Methods of Measurement.- 5.1. T1 Measurements.- 5.2. Nuclear Overhauser Enhancement Measurements.- 5.3. T2 Measurement, and Other Uses of Spin Echoes.- 6. Line Broadening Due to Chemical Exchange.- 6.1. T1 in the Presence of Chemical Exchange.- 7. Paramagnetic Interactions.- 7.1. Kinetics.- 7.2. Paramagnetic Contributions to T1 and T2.- 8. Two-Dimensional NMR.- 8.1. Shift-Correlation Experiments.- 8.2. J-Resolved Two-Dimensional Spectroscopy.- References.- 6 Hydrogen and Its Isotopes: Hydrogen, Deuterium, and Tritium.- 1. Introduction.- 2. Experimental Techniques.- 3. Hydrogen or the Proton, or Protium.- 3.1. Strong or Weak Hydrogen Bonds.- 3.2. Ionic Solvation.- 3.3. Chemical Shifts of Adducts.- 3.4. Hydrogen on Carbon.- 3.5. Hydride Protons.- 3.6. Dynamic Processes.- 4. Deuterium.- 4.1. Deuterium NMR in Isotropic Liquids.- 4.2. Deuterium NMR of Liquid Crystalline Phases.- 4.3. Deuterium NMR in Solids and Heterogeneous Systems.- 5. Tritium.- References.- 7 The Alkali and Alkaline Earth Metals: Lithium, Sodium, Potassium, Rubidium, Cesium, Beryllium, Magnesium, Calcium, Strontium, and Barium.- 1. Introduction to Groups I and II.- 2. Experimental Techniques.- 3. Aqueous Solutions of Simple Salts.- 3.1. Nuclear Relaxation.- 3.2. Chemical Shifts.- 4. Mixed and Nonaqueous Solutions of Simple Salts.- 4.1. Nuclear Relaxation.- 4.2. Chemical Shifts.- 5. Complexes Between the Cations and Various Types of Ligands.- 5.1. Complexes with Low-Molecular-Weight Compounds.- 5.2. Complexes with Synthetic Polymeric Ligands.- 5.3. Complexes with Biopolymers.- 5.4. Cations in Liquid Crystals.- 6. Group I and II Metal Organic Compounds.- 6.1. Lithium Organic Compounds.- 6.2. Beryllium Covalent Compounds.- References.- 8 Boron.- 1. Nuclear Properties and General Considerations.- 2. Trigonal and Tetrahedral Compounds.- 2.1. Chemical Shifts.- 2.2. Coupling Constants.- 2.3. Relaxation Studies.- 3. Polyhedral Boron-Containing Species.- 3.1. General Considerations.- 3.2. Boron Chemical Shifts.- 3.3. Coupling Constants.- 3.4. Relaxation Times.- 3.5. Polyhedral Species—Nuclei Other than Boron.- 3.6. Fluxionality.- References.- 9 Aluminum, Gallium, Indium, and Thallium.- 1. The Nuclear Properties of Al, Ga, and In, the Quadrupolar Nuclei.- 2. Aluminum.- 2.1. Operational Techniques.- 2.2. Aluminum-27 NMR Parameters.- 2.3. Some Observations on the Parameters.- 3. Gallium.- 3.1. Operational Techniques.- 3.2. Gallium-69 and Gallium-71 NMR Parameters.- 4. Indium.- 4.1. Indium-115 NMR Parameters.- 5. Thallium.- References.- 10 Carbon.- 11 Silicon, Germanium, Tin, and Lead.- 1. Introduction.- 2. Experimental Aspects.- 3. Chemical Shifts.- 3.1. Isotope Effects.- 3.2. Solvent and Temperature Effects.- 3.3. Chemical Shift Patterns.- 3.4. Factors Influencing Shielding.- 3.5. Chemical Shifts in Specific Classes of Compound.- 4. Coupling Constants.- 4.1. One-Bond Couplings.- 4.2. Two-Bond Couplings.- 4.3. Three-Bond Couplings.- 5. Relaxation Behavior.- 6. Miscellaneous and Solid State Work.- References.- 12 Nitrogen.- 1. Nitrogen NMR Spectroscopy.- 1.1. Nitrogen Referencing.- 1.2. Medium Effects.- 1.3. Solid State Measurements in High Resolution.- 1.4. Isotope Effects and Tracer Studies.- 2. 15N NMR Spectroscopy.- 2.1. 15N Relaxation and NOE Factors.- 2.2. Sensitivity Enhancement.- 3. 14N NMR Spectroscopy.- 3.1. 14N Quadrupolar Relaxation.- 4. Patterns of Nitrogen Shielding.- 4.1. Nitrogen NMR Criteria of Structure.- 4.2. Inorganic Azines and Azenes.- 4.3. Coordination Shifts.- 5. Nitrogen Spin-Spin Coupling.- 6. Dynamics.- 7. Biomolecules.- References.- 13 Phosphorus to Bismuth.- 1. Phosphorus-31.- 1.1. Introduction.- 1.2. Spin Lattice Relaxation (T1).- 1.3. Chemical Shifts.- 1.4. Coupling Constants.- 2. Arsenic-75, Antimony-121,123 and Bismuth-209.- References.- 14 Oxygen.- 1. Introduction.- 2. Experimental Aspects.- 3. Chemical Shifts.- 4. Spin Coupling.- 5. Relaxation Behavior.- 6. Applications.- 7. The Solid State.- References.- 15 Sulfur, Selenium, and Tellurium.- 1. Introduction.- 2. Sulfur.- 3. Selenium and Tellurium.- 3.1. Chemical Shifts.- 3.2. Coupling Constants.- 3.3. Relaxation Behavior.- 3.4. Applications.- References.- 16 Fluorine.- 1. 19F NMR Measurements.- 2. 19F Chemical Shifts.- 2.1. Absolute Shielding Scale.- 2.2. Empirical Patterns of 19F Nuclear Shielding.- 2.3. Anisotropy of the 19F Shielding Tensor.- 3. Spin-Spin Coupling Involving 19F.- 4. 19F Relaxation.- References.- 17 The Quadrupolar Halides: Chlorine, Bromine and Iodine.- 1. Introduction.- 2. Experimental Techniques.- 3. NMR Parameters.- 3.1. Covalent Compounds.- 3.2. Ionic Solutions.- References.- 18 The Noble Gases.- 1. Introduction.- 2. 129Xe NMR Studies of Bonding and Structure of Xenon Compounds.- 2.1. 129Xe Chemical Shifts.- 2.2. Spin-Spin Coupling to Xenon.- 3. Probing Nonspecific Intermolecular Interactions with Noble Gas Nuclei.- 3.1. Medium Shifts.- 3.2. Relaxation Times.- References.- 19 Early Transition Metals, Lanthanides and Actinides.- 1. Introduction.- 2. Group IIIb.- 2.1. Scandium.- 2.2. Yttrium.- 2.3. Lanthanum.- 2.4. The Lanthanides.- 2.5. Actinium and the Actinides.- 3. Group IVb: Titanium, Zirconium, and Hafnium.- 4. Group Vb.- 4.1. Vanadium.- 4.2. Niobium.- 4.3. Tantalum.- 5. Group VIb.- 5.1. Chromium.- 5.2. Molybdenum.- 5.3. Tungsten.- 6. Group VIIb.- 6.1. Manganese.- 6.2. Technetium.- 6.3. Rhenium.- References.- 20 Group VIII Transition Metals.- 1. Introduction.- 2. Observation.- 2.1. Relaxation Behavior.- 2.2. Methods of Observation.- 3. Chemical Shifts.- 3.1. Evaluation of Chemical Shifts.- 3.2. Results.- 3.3. Theoretical Approaches.- 3.4. Empirical Correlations.- 3.5. Effects of the Molecular Environment and Isotopes.- 4. Spin-Spin Coupling.- 4.1. Sign Determinations.- References.- 21 Post-Transition Metals, Copper to Mercury.- 1. Introduction.- 2. Observation.- 2.1. 63Cu and 65Cu.- 2.2. 67Zn.- 2.3. 107Ag and 109Ag.- 2.4. 111Cd and 113Cd.- 2.5. 197Au.- 2.6. 199Hg and 201Hg.- 3. Chemical Shifts.- 3.1. Results.- 3.2. Discussion.- 4. Spin-Spin Coupling.- 4.1. Sign Determinations.- References.- 22 NMR Spectroscopy in Bioinorganic Chemistry.- 1. Introduction.- 2. Some Examples of Biological Applications: Isotope Shifts in 31P NMR.- 3. Sodium Transport Through Membranes Using 23Na Resonance.- 4. Active Site Interactions in Fluorine-Labeled ?-Chymotrypsin.- 5. 113Cd Studies of Alkaline Phosphatase.- 6. 31P NMR in Living Tissue.- 7. Ion Binding to Cytochrome c Studied by Nuclear Magnetic Quadrupole Relaxation.- 8. Deuterium Label Studies of Membranes.- 9. Direct Determination of Correlation Times in Enzyme Complexes Involving Monovalent Cations and Paramagnetic Centers.- Index of Reviews.- References.- 23 Biomedical NMR.- 1. Biomedical NMR.- 2. NMR Imaging.- 3. Localized NMR Spectroscopy.- 4. Further Applications.- References.- Symbols and Abbreviations.- SI Units and Fundamental Constants.- Appendix: NMR Properties of the Elements.