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

J 2020

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

FOROUTANNEJAD, Cina; Jan VÍCHA a Abhik GHOSH

Základní údaje

Originální název

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

Autoři

FOROUTANNEJAD, Cina; Jan VÍCHA a Abhik GHOSH

Vydání

Physical Chemistry Chemical Physics, Cambridge, Royal Society of Chemistry, 2020, 1463-9076

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 3.676

Označené pro přenos do RIV

Ano

Kód RIV

RIV/00216224:14310/20:00116802

Organizační jednotka

Přírodovědecká fakulta

Klíčová slova anglicky

zeta basis set; triple-zeta; electrons delocalized; heavy-atoms; metallabenzenes; anisotropy

Štítky

14313010, 143160, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 13. 2. 2023 12:50, Mgr. Marie Novosadová Šípková, DiS.

Anotace

V originále

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 sigma-type Craig-Mobius 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 sigma(Os-C) bonding orbitals and the pi*(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.

Návaznosti

LM2015085, projekt VaV

Název: CERIT Scientific Cloud (Akronym: CERIT-SC)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, CERIT Scientific Cloud

90042, velká výzkumná infrastruktura

Název: CESNET II

90070, velká výzkumná infrastruktura

Název: IT4Innovations

Citovat

FOROUTANNEJAD, Cina; Jan VÍCHA a Abhik GHOSH. Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives. Physical Chemistry Chemical Physics. Cambridge: Royal Society of Chemistry, 2020, roč. 22, č. 19, s. 10863-10869. ISSN 1463-9076. Dostupné z: https://doi.org/10.1039/d0cp01481h.

@article{1688720,
   author = {Foroutannejad, Cina and Vícha, Jan and Ghosh, Abhik},
   article_location = {Cambridge},
   article_number = {19},
   doi = {https://doi.org/10.1039/d0cp01481h},
   keywords = {zeta basis set; triple-zeta; electrons delocalized; heavy-atoms; metallabenzenes; anisotropy},
   language = {eng},
   issn = {1463-9076},
   journal = {Physical Chemistry Chemical Physics},
   title = {Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives},
   url = {https://doi.org/10.1039/D0CP01481H},
   volume = {22},
   year = {2020}
}

TY  - JOUR
ID  - 1688720
AU  - Foroutannejad, Cina - Vícha, Jan - Ghosh, Abhik
PY  - 2020
TI  - Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives
JF  - Physical Chemistry Chemical Physics
VL  - 22
IS  - 19
SP  - 10863-10869
EP  - 10863-10869
PB  - Royal Society of Chemistry
SN  - 14639076
KW  - zeta basis set
KW  - triple-zeta
KW  - electrons delocalized
KW  - heavy-atoms
KW  - metallabenzenes
KW  - anisotropy
UR  - https://doi.org/10.1039/D0CP01481H
L2  - https://doi.org/10.1039/D0CP01481H
N2  - 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 sigma-type Craig-Mobius 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 sigma(Os-C) bonding orbitals and the pi*(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.
ER  -

FOROUTANNEJAD, Cina; Jan VÍCHA a Abhik GHOSH. Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives. \textit{Physical Chemistry Chemical Physics}. Cambridge: Royal Society of Chemistry, 2020, roč.~22, č.~19, s.~10863-10869. ISSN~1463-9076. Dostupné z: https://doi.org/10.1039/d0cp01481h.

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