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Institutional Subscription. Free Shipping Free global shipping No minimum order. List of Contributors Preface 1. The Paramagnetic Shift I. Introduction II.
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The Paramagnetic Linewidth I. Electron-Spin Relaxation References 3. Spin Delocalization and Electronic Structure I. Spin Delocalization and Spin Polarization V. Metal-Ligand Covalency References 4. Analysis of Isotropic Shifts I.
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Spin Distribution in Organic Ligands I. Conclusion References 6.
Spin Distribution in Organometallic Compounds I. Bis-Arene Organometallics: Results V.
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Conclusions References 7. Stereochemistry and Structural and Electronic Equilibria I. Spin Equilibria Appendix References 8. The difference between the chemical shift of a given nucleus in a diamagnetic vs paramagnetic environments is called the isotropic shift. The isotropic chemical shift for nickelocene is ppm, which is the difference between the observed shift ca.
NMR of Paramagnetic Molecules
The isotropic shift contains contributions from the pseudocontact called dipolar and contact also called scalar terms. Isotropic shifts result from two mechanisms, contact shifts and pseudocontact shifts. Both effects operate simultaneously but one or the other term can be dominant. Contact shifts result from spin polarization conveyed through the molecular orbitals of the molecule. Pseudocontact shifts result from the magnetic field emanating from the paramagnetic center.
The effect of the contact term arises from transfer of spin polarization to the observed nucleus.
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Spin polarization is a consequence of the very strong electron-nuclear NMR detected interaction. This coupling, also known by EPR spectroscopists as hyperfine coupling , is on the order of MHz, vs the usual internuclear J coupling observed in conventional NMR spectra, which are on the order of a few Hz.
Owing to rapid spin relaxation, the electron-nuclear coupling is not observed in the NMR spectrum, so the affected nuclear resonance appears at the average of the two coupled energy states, weighted according to their spin populations. Given the magnitude of the coupling, the Boltzmann population of these spin state are not close to , leading to net spin polarization on the affected NMR nucleus, hence a relatively large contact shifts.
The effect of the pseudocontact term arises magnetic anisotropy of the paramagnetic center reflected in g-anisotropy in the EPR spectrum. This anisotropy creates a magnetic field which supplements that of the instrument's magnet.
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