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

Result code in 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>

Alternative codes found

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

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10401 - Organic chemistry

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

2020

Confidentiality

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

Name of the periodical

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

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Volume of the periodical

26

Issue of the periodical within the volume

40

Country of publishing house

DE - GERMANY

Number of pages

5

Pages from-to

8698-8702

UT code for WoS article

000539657000001

EID of the result in the Scopus database

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