By Ivano Bertini, Claudio Luchinat, Giacomo Parigi, Enrico Ravera
NMR of Paramagnetic Molecules: purposes to Metallobiomolecules and types, moment Edition is a self-contained, finished reference for chemists, physicists, and lifestyles scientists whose examine comprises reading paramagnetic compounds. because the earlier variation of this publication used to be released, there were many developments within the box of paramagnetic NMR spectroscopy. This thoroughly up to date and improved version comprises the newest primary idea and strategies for mastery of this analytical strategy. clients will how one can interpret the NMR spectra of paramagnetic molecules, increase experimental options, and boost their figuring out of the underlying thought and applications.
- Reflects all advances within the box in a totally up-to-date new edition
- Presents new fabric on self-orientation residual dipolar couplings, sturdy country NMR, dynamic nuclear polarization, and paramagnetic restraints for constitution calculations
- Includes details proper to paramagnetic molecules, metallobiomolecules, paramagnetic compounds, and paramagnetic NMR spectroscopy
- Presents particular examples of paramagnetic inorganic species and experimental concepts for constitution characterization
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Extra resources for NMR of Paramagnetic Molecules. Applications to Metallobiomolecules and Models
Type s orbitals have maximal electron density on the nucleus, as their wavefunction is of the type exp(–r), where r is the electron–nucleus distance. 1 The unpaired electron in a 2p orbital affects the distribution of the two paired electrons in a 1s orbital. 2 THE MAGNETIC NUCLEUS–UNPAIRED ELECTRON INTERACTION 27 MO containing an s orbital, there will be a finite probability that the electron resides on that nucleus. The amount of unpaired electrons residing on the nucleus is the spin density ρ at the nucleus.
C ρH values in parentheses, estimated from Eq. 59). d Absolute values (obtained from relaxation data). 1) show large hyperfine coupling constants when unpaired electrons are located in the eg orbitals, which have the correct symmetry for σ bonding. The data for Cu(H 2 O)62+ and Ni(H 2 O)2+ 6 demonstrate this clearly. It is obvious that direct delocalization through metal–oxygen σ bonding involving oxygen s orbitals gives rise to quite sizable spin density on the oxygen nucleus. 1), there is an excess of MS = –½ occupancy (positive spin density).
The amount of unpaired electrons residing on the nucleus is the spin density ρ at the nucleus. The spin density at the nucleus or in any other point is, in general, not just the positive quantity arising from the direct delocalization explained above, but also contains contributions due to spin polarization of paired electrons. The latter mechanism accounts for the presence of spin density on nuclei when the unpaired electron occupies a d orbital, which, like the p orbital, has a node at the nucleus.