High-Frequency C-13 and Si-29 NMR Chemical Shifts in Diamagnetic Low-Valence Compounds of TII and Pb-II: Decisive Role of Relativistic Effects

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F16%3A00458931" target="_blank" >RIV/61388963:_____/16:00458931 - isvavai.cz</a>
Alternative codes found
RIV/00216224:14740/16:00088696
Result on the web
<a href="http://dx.doi.org/10.1021/acs.inorgchem.5b02689" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.5b02689</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.5b02689" target="_blank" >10.1021/acs.inorgchem.5b02689</a>

Result language
angličtina
Original language name
High-Frequency C-13 and Si-29 NMR Chemical Shifts in Diamagnetic Low-Valence Compounds of TII and Pb-II: Decisive Role of Relativistic Effects
Original language description
The C-13 and Si-29 NMR signals of ligand atoms directly bonded to TII or Pb-II heavy-element centers are predicted to resonate at very high frequencies, up to 400 ppm for C-13 and over 1000 ppm for Si-29, outside the typical experimental NMR chemical-shift ranges for a given type of nuclei. The large C-13 and Si-29 NMR chemical shifts are ascribed to sizable relativistic spin-orbit effects, which can amount to more than 200 ppm for C-13 and more than 1000 ppm for Si-29, values unexpected for diamagnetic compounds of the main group elements. The origin of the vast spin-orbit contributions to the C-13 and Si-29 NMR shifts is traced to the highly efficient 6p -> 6p* metal-based orbital magnetic couplings and related to the 6p orbital-based bonding together with the low-energy gaps between the occupied and virtual orbital subspaces in the subvalent TII and Pb-II compounds. New NMR spectral regions for these compounds are suggested based on the fully relativistic density functional theory calculations in the Dirac-Coulomb framework carefully calibrated on the experimentally known NMR data for TII and Pb-II complexes.
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2016
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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