Experimental and Theoretical Evidence of Spin‐Orbit Heavy Atom on the Light Atom 1H NMR Chemical Shifts Induced through H⋅⋅⋅I− Hydrogen Bond

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00532381" target="_blank" >RIV/61388963:_____/20:00532381 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216275:25310/20:39916643 RIV/70883521:28610/20:63526495

Výsledek na webu

<a href="https://doi.org/10.1002/chem.202001532" target="_blank" >https://doi.org/10.1002/chem.202001532</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202001532" target="_blank" >10.1002/chem.202001532</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Experimental and Theoretical Evidence of Spin‐Orbit Heavy Atom on the Light Atom 1H NMR Chemical Shifts Induced through H⋅⋅⋅I− Hydrogen Bond

Popis výsledku v původním jazyce

Spin‐orbit (SO) heavy‐atom on the light‐atom (SO‐HALA) effect is the largest relativistic effect caused by a heavy atom on its light‐atom neighbors, leading, for example, to unexpected NMR chemical shifts of 1H, 13C, and 15N nuclei. In this study, a combined experimental and theoretical evidence for the SO‐HALA effect transmitted through hydrogen bond is presented. Solid‐state NMR data for a series of 4‐dimethylaminopyridine salts containing I−, Br− and Cl− counter ions were obtained experimentally and by theoretical calculations. A comparison of the experimental chemical shifts with those calculated by a standard DFT methodology without the SO contribution to the chemical shifts revealed a remarkable error of the calculated proton chemical shift of a hydrogen atom that is in close contact with the iodide anion. The addition of the relativistic SO correction in the calculations significantly improves overall agreement with the experiment and confirms the propagation of the SO‐HALA effect through hydrogen bonds.

Název v anglickém jazyce

Experimental and Theoretical Evidence of Spin‐Orbit Heavy Atom on the Light Atom 1H NMR Chemical Shifts Induced through H⋅⋅⋅I− Hydrogen Bond

Popis výsledku anglicky

Spin‐orbit (SO) heavy‐atom on the light‐atom (SO‐HALA) effect is the largest relativistic effect caused by a heavy atom on its light‐atom neighbors, leading, for example, to unexpected NMR chemical shifts of 1H, 13C, and 15N nuclei. In this study, a combined experimental and theoretical evidence for the SO‐HALA effect transmitted through hydrogen bond is presented. Solid‐state NMR data for a series of 4‐dimethylaminopyridine salts containing I−, Br− and Cl− counter ions were obtained experimentally and by theoretical calculations. A comparison of the experimental chemical shifts with those calculated by a standard DFT methodology without the SO contribution to the chemical shifts revealed a remarkable error of the calculated proton chemical shift of a hydrogen atom that is in close contact with the iodide anion. The addition of the relativistic SO correction in the calculations significantly improves overall agreement with the experiment and confirms the propagation of the SO‐HALA effect through hydrogen bonds.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

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

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

—

Svazek periodika

26

Číslo periodika v rámci svazku

40

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

5

Strana od-do

8698-8702

Kód UT WoS článku

000539657000001

EID výsledku v databázi Scopus

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