Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F70883521%3A28610%2F20%3A63526490" target="_blank" >RIV/70883521:28610/20:63526490 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216224:14310/20:00116802

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2020/CP/D0CP01481H#!divAbstract" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2020/CP/D0CP01481H#!divAbstract</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0cp01481h" target="_blank" >10.1039/d0cp01481h</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives

Popis výsledku v původním jazyce

We have studied the magnetic response properties and aromaticity of osmium metallacycles by means of scalar-relativistic (1c) and fully relativistic (4c) density functional theory computations. For osmabenzene, whose aromatic character is controversial, a topological analysis of the current density has revealed the presence of a unique σ-type Craig-Möbius magnetic aromaticity. We show that the partially filled osmium valence shell induces a large paratropic current, which may interfere with certain methods commonly used to analyze aromaticity, in particular NICS. Further, we show that the extreme deshielding of the light atoms in the vicinity of the osmium atoms in osmapentalene derivatives is not a consequence of aromaticity but can be explained by paramagnetic couplings between σOs - C bonding orbitals and the π∗Os orbitals. We demonstrate that variations in the orientation of the induced magnetic currents through the molecule dictates the alternating signs of the spin-orbit contribution to the NMR chemical shift. This journal is © the Owner Societies.

Název v anglickém jazyce

Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives

Popis výsledku anglicky

We have studied the magnetic response properties and aromaticity of osmium metallacycles by means of scalar-relativistic (1c) and fully relativistic (4c) density functional theory computations. For osmabenzene, whose aromatic character is controversial, a topological analysis of the current density has revealed the presence of a unique σ-type Craig-Möbius magnetic aromaticity. We show that the partially filled osmium valence shell induces a large paratropic current, which may interfere with certain methods commonly used to analyze aromaticity, in particular NICS. Further, we show that the extreme deshielding of the light atoms in the vicinity of the osmium atoms in osmapentalene derivatives is not a consequence of aromaticity but can be explained by paramagnetic couplings between σOs - C bonding orbitals and the π∗Os orbitals. We demonstrate that variations in the orientation of the induced magnetic currents through the molecule dictates the alternating signs of the spin-orbit contribution to the NMR chemical shift. This journal is © the Owner Societies.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

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

2020

Kód důvěrnosti údajů

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

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Svazek periodika

22

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

7

Strana od-do

10863-10869

Kód UT WoS článku

000537251100044

EID výsledku v databázi Scopus

2-s2.0-85085265360