NMR of Paramagnetic Molecules - 1st Edition - ISBN: 9780124345508, 9781483272450

NMR of Paramagnetic Molecules

1st Edition

Principles and Applications

Editors: G. N. La Mar W. Dew. Horrocks R. H. Holm
eBook ISBN: 9781483272450
Imprint: Academic Press
Published Date: 28th January 1973
Page Count: 694
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Description

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.

Table of Contents


List of Contributors

Preface

1. The Paramagnetic Shift

I. Introduction

II. High-Resolution Nuclear Magnetic Resonance in Diamagnetic Systems

III. Electron Paramagnetic Resonance in the Hydrogen Atom

IV. High-Resolution Nuclear Magnetic Resonance in a Simple Paramagnetic System

V. General Treatment of High-Resolution Nuclear Magnetic Resonance Shifts in Paramagnetic Systems

VI. Application of the General Theory

VII. Other Factors Affecting the Paramagnetic Shift

VIII. Summary

Appendix: Density Matrix Theory

References

2. The Paramagnetic Linewidth

I. Introduction

II. Magnetic Relaxation and the NMR Line Shape

III. Mechanisms of Nuclear Spin-Lattice Relaxation

IV. Electron-Spin Relaxation

References

3. Spin Delocalization and Electronic Structure

I. Introduction

II. Spin Density and Electron Correlation

III. Hyperfine Coupling Constants and Spin Density

IV. Spin Delocalization and Spin Polarization

V. Metal-Ligand Covalency

References

4. Analysis of Isotropic Shifts

I. Introduction

II. Determination of the Origin of Observed Shifts

III. Characterization of Contact Shifts by Quantum Mechanical Models

References

5. Spin Distribution in Organic Ligands

I. Introduction

II. Qualitative Applications of Ligand Spin Density Measurements

III. The Quantitative Assessment of Spin Density Distributions

IV. The Effect of Other Ligands on Spin Density Distributions

V. Conclusion

References

6. Spin Distribution in Organometallic Compounds

I. Introduction

II. Bis-π-Cyclopentadienyl Complexes: Results

III. Discussion of Bis-π-Cyclopentadienyl Complexes

IV. Bis-Arene Organometallics: Results

V. Discussion of Bis-Arene Organometallics

VI. Contact Shifts of Other Organometallics

VII. Conclusions

References

7. Stereochemistry and Structural and Electronic Equilibria

I. Introduction

II. Stereochemistry and Structural Equilibria

III. Spin Equilibria

Appendix

References

8. Dynamics of Intramolecular Rearrangements

I. Introduction

II. Metal-Centered Rearrangements

III. Ligand-Centered Rearrangements

References

9. Solvation and the Second Coordination Sphere

I. Introduction

II. Theory

III. Applications

References

10. Novel Structural Studies in Solution

I. Introduction

II. Ion Pairing in Solution

III. Orbital Ground State Symmetry

References

11. Biological Applications

I. Introduction

II. PMR Characteristics of Proteins

III. Contact Shifts Induced by Extrinsic Ions

IV. Heme Proteins

V. Iron-Sulfur Proteins

VI. Conclusions

References

12. Lanthanide Shift Reagents and Other Analytical Applications

I. Introduction

II. Lanthanide Shift Reagents

III. Spin Decoupling and Relaxation Enhancement

IV. Determination of Relative Stability Constants

References

13. Lanthanide and Actinide Complexes

I. Introduction

II. Important General Features of the Electronic Structure of fn Systems

III. Experimental Results

IV. The Origin of the Pure Fermi Contact Contributions

References

14. Nuclei Other Than Protons

I. Introduction—Scope and General Overview

II. Distinctive Features of Heteronuclear NMR

III. Survey of Experimental Results

Appendix

References

15. NMR Studies of Organic Radicals

I. Introduction

II. Kinetics of Reactions Involving Diamagnetic and Paramagnetic Molecules

III. Hyperfine Coupling Constants from NMR Spectra

IV. NMR of Polyradicals

V. Radical-Solvent Interactions

References

16. Some Notes Added in Proof

I. Introduction

II. Analysis of Isotropic Shifts

III. Stereochemistry

IV. Intramolecular Rearrangements

V. Biological Applications

VI. Shift Reagents and Analytical Applications

VII. Deuterium NMR

References

Author Index

Subject Index

Details

No. of pages:
694
Language:
English
Copyright:
© Academic Press 1973
Published:
Imprint:
Academic Press
eBook ISBN:
9781483272450

About the Editor

G. N. La Mar

W. Dew. Horrocks

R. H. Holm