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

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/00216224:14740/16:00088696

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

—

Svazek periodika

55

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

1770-1781

Kód UT WoS článku

000370395000049

EID výsledku v databázi Scopus

2-s2.0-84958811344