La Mar / Horrocks / Holm NMR of Paramagnetic Molecules

Principles and Applications
1. Auflage 2013
ISBN: 978-1-4832-7245-0
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 694 Seiten, Web PDF

NMR of Paramagnetic Molecules: Principles and Applications is a compendium of papers that discusses the physical principles behind the technique of nuclear magnetic resonance, as well as, evaluates the scope and limitation of the applications of NMR in chemistry and biology. These papers emphasize the applications of the technique in chemistry and biochemistry where it widely used, particularlyon NMR experiments in the liquid state. Some papers describe the theoretical factors governing the resonance position and linewidth, and then also interpret magnetic resonance parameters in terms of electronic structure. Another paper investigates the gap between the mathematical complexities of earlier experiments and the operational aspects of chemical information from the spectra. Examples show studies in biochemical molecules and process in events where contact interactions are present either as a result of intrinsic molecular paramagnetism or are just induced through the addition of suitable paramagnetic probes. One paper presents the definitive and controversial results involving stereochemistry and deuterium NMR. This collection of papers will prove useful for nuclear physicists, researchers, and academicians in the field of nuclear physics.

Autoren/Hrsg.

La Mar, G. N.

Horrocks, W. Dew.

Holm, R. H.

Inhaltsverzeichnis

1;Front Cover;1
2;NMR of Paramagnetic Molecules: Principles and Applications;4
3;Copyright Page;5
4;Table of Contents;6
5;LIST OF CONTRIBUTORS;12
6;PREFACE;14
7;Chapter 1. The Paramagnetic Shift;18
7.1;I. Introduction;19
7.2;II. High-Resolution Nuclear Magnetic Resonance in Diamagnetic Systems;20
7.3;III. Electron Paramagnetic Resonance in the Hydrogen Atom;21
7.4;IV. High-Resolution Nuclear Magnetic Resonance in a Simple Paramagnetic System;26
7.5;V. General Treatment of High-Resolution Nuclear Magnetic Resonance Shifts in Paramagnetic Systems;29
7.6;VI. Application of the General Theory;39
7.7;VII. Other Factors Affecting the Paramagnetic Shift;58
7.8;VIII. Summary;62
7.9;Appendix: Density Matrix Theory;62
7.10;References;68
8;Chapter 2. The Paramagnetic Linewidth;70
8.1;I. Introduction;70
8.2;II. Magnetic Relaxation and the NMR Line Shape;71
8.3;III. Mechanisms of Nuclear Spin–Lattice Relaxation;89
8.4;IV. Electron–Spin Relaxation;94
8.5;References;98
9;Chapter 3. Spin Delocalization and Electronic Structure;102
9.1;I. Introduction;103
9.2;II. Spin Density and Electron Correlation;104
9.3;III. Hyperfine Coupling Constants and Spin Density;110
9.4;IV. Spin Delocalization and Spin Polarization;120
9.5;V. Metal–Ligand Covalency;135
9.6;References;140
10;Chapter 4. Analysis of Isotropic Shifts;144
10.1;I. Introduction;145
10.2;II. Determination of the Origin of Observed Shifts;151
10.3;III. Characterization of Contact Shifts by Quantum Mechanical Models;174
10.4;References;192
11;Chapter 5. Spin Distribution in Organic Ligands;196
11.1;I. Introduction;196
11.2;II. Qualitative Applications of Ligand Spin Density Measurements;202
11.3;III. The Quantitative Assessment of Spin Density Distributions;217
11.4;IV. The Effect of Other Ligands on Spin Density Distributions;222
11.5;V. Conclusion;230
11.6;References;231
12;Chapter 6. Spin Distribution in Organometallic Compounds;234
12.1;I. Introduction;235
12.2;II. Bis-p-Cyclopentadienyl Complexes: Results;236
12.3;III. Discussion of Bis-p-Cyclopentadienyl Complexes;239
12.4;IV. Bis-Arene Organometallics: Results;249
12.5;V. Discussion of Bis-Arene Organometallics;252
12.6;VI. Contact Shifts of Other Organometallics;255
12.7;VII. Conclusions;257
12.8;References;258
13;Chapter 7. Stereochemistry and Structural and Electronic Equilibria;260
13.1;I. Introduction;260
13.2;II. Stereochemistry and Structural Equilibria;264
13.3;III. Spin Equilibria;333
13.4;Appendix;342
13.5;References;343
14;Chapter 8. Dynamics of Intramolecular Rearrangements;350
14.1;I. Introduction;351
14.2;II. Metal-Centered Rearrangements;354
14.3;III. Ligand-Centered Rearrangements;371
14.4;References;384
15;Chapter 9. Solvation and the Second Coordination Sphere;388
15.1;I. Introduction;389
15.2;II. Theory;390
15.3;III. Applications;395
15.4;References;402
16;Chapter 10. Novel Structural Studies in Solution;404
16.1;I. Introduction;404
16.2;II. Ion Pairing in Solution;405
16.3;III. Orbital Ground State Symmetry;425
16.4;References;435
17;Chapter 11. Biological Applications;438
17.1;I. Introduction;439
17.2;II. PMR Characteristics of Proteins;439
17.3;III. Contact Shifts Induced by Extrinsic Ions;443
17.4;IV. Heme Proteins;452
17.5;V. Iron–Sulfur Proteins;475
17.6;VI. Conclusions;491
17.7;References;492
18;Chapter 12. Lanthanide Shift Reagents and Other Analytical Applications;496
18.1;I. Introduction;496
18.2;II. Lanthanide Shift Reagents;498
18.3;III. Spin Decoupling and Relaxation Enhancement;526
18.4;IV. Determination of Relative Stability Constants;531
18.5;References;534
19;Chapter 13. Lanthanide and Actinide Complexes;538
19.1;I. Introduction;539
19.2;II. Important General Features of the Electronic Structure of fn Systems;540
19.3;III. Experimental Results;546
19.4;IV. The Origin of the Pure Fermi Contact Contributions;562
19.5;References;566
20;Chapter 14. Nuclei Other Than Protons;572
20.1;I. Introduction—Scope and General Overview;573
20.2;II. Distinctive Features of Heteronuclear NMR;574
20.3;III. Survey of Experimental Results;584
20.4;Appendix;600
20.5;References;607
21;Chapter 15. NMR Studies of Organic Radicals;612
21.1;I. Introduction;612
21.2;II. Kinetics of Reactions Involving Diamagnetic and Paramagnetic Molecules;614
21.3;III. Hyperfine Coupling Constants from NMR Spectra;621
21.4;IV. NMR of Polyradicals;636
21.5;V. Radical-Solvent Interactions;641
21.6;References;641
22;Chapter 16. Some Notes Added in Proof;644
22.1;I. Introduction;645
22.2;II. Analysis of Isotropic Shifts;645
22.3;III. Stereochemistry;647
22.4;IV. Intramolecular Rearrangements;649
22.5;V. Biological Applications;650
22.6;VI. Shift Reagents and Analytical Applications;652
22.7;VII. Deuterium NMR;655
22.8;References;657
23;AUTHOR INDEX;660
24;SUBJECT INDEX;684