Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F15%3A00080688" target="_blank" >RIV/00216224:14740/15:00080688 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/15:00444353

Výsledek na webu

<a href="http://dx.doi.org/10.1021/ct501089z" target="_blank" >http://dx.doi.org/10.1021/ct501089z</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/ct501089z" target="_blank" >10.1021/ct501089z</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes

Popis výsledku v původním jazyce

The significant role of the relativistic effects in altering the NMR chemical shifts of light nuclei in heavy-element compounds has been recognized for a long time, however full understanding of this phenomenon in relation to the electronic structure hasnot been achieved. In this study, the recently observed qualitative differences between the platinum and gold compounds in the magnitude and the sign of spin-orbit-induced (SO) nuclear magnetic shielding at the vicinal light atom (13C, 15N), sigmaSO(LA), are explained by the contractions of 6s and 6p atomic orbitals in Au complexes, originating in the larger Au nuclear charge and stronger scalar relativistic effects in gold complexes. This leads to the chemical activation of metal 6s and 6p atomic orbitals in Au complexes and their larger participation in bonding with the ligand, which modulates the propagation of metal-induced SO effects on the NMR signal of the LA via the Spin-Orbit/Fermi Contact (SO/FC) mechanism.

Název v anglickém jazyce

Understanding the electronic factors responsible for ligand spin-orbit NMR shielding in transition-metal complexes

Popis výsledku anglicky

The significant role of the relativistic effects in altering the NMR chemical shifts of light nuclei in heavy-element compounds has been recognized for a long time, however full understanding of this phenomenon in relation to the electronic structure hasnot been achieved. In this study, the recently observed qualitative differences between the platinum and gold compounds in the magnitude and the sign of spin-orbit-induced (SO) nuclear magnetic shielding at the vicinal light atom (13C, 15N), sigmaSO(LA), are explained by the contractions of 6s and 6p atomic orbitals in Au complexes, originating in the larger Au nuclear charge and stronger scalar relativistic effects in gold complexes. This leads to the chemical activation of metal 6s and 6p atomic orbitals in Au complexes and their larger participation in bonding with the ligand, which modulates the propagation of metal-induced SO effects on the NMR signal of the LA via the Spin-Orbit/Fermi Contact (SO/FC) mechanism.

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

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2015

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

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Svazek periodika

11

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

1509-1517

Kód UT WoS článku

000353176500018

EID výsledku v databázi Scopus

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