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

Result code in 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>
Alternative codes found
RIV/00216224:14310/20:00116802
Result on the web
<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>

Result language
angličtina
Original language name
Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives
Original language description
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.
Czech name
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Czech description
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Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry

Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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