Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F24%3A00135949" target="_blank" >RIV/00216224:14310/24:00135949 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04425" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04425</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.3c04425" target="_blank" >10.1021/acs.inorgchem.3c04425</a>
Alternative languages
Result language
angličtina
Original language name
Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways
Original language description
Theoretical interpretation of hyperfine interactions was pioneered in the 1950s-1960s by the seminal works of McConnell, Karplus, and others for organic radicals and by Watson and Freeman for transition-metal (TM) complexes. In this work, we investigate a series of octahedral Ru(III) complexes with aromatic ligands to understand the mechanism of transmission of the spin density from the d-orbital of the metal to the s-orbitals of the ligand atoms. Spin densities and spin populations underlying ligand hyperfine couplings are analyzed in terms of pi-conjugative or sigma-hyperconjugative delocalization vs. spin polarization based on symmetry considerations and restricted open-shell vs. unrestricted wave function analysis. The transmission of spin density is shown to be most efficient in the case of symmetry-allowed pi-conjugative delocalization, but when the pi-conjugation is partially or fully symmetry-forbidden, it can be surpassed by the sigma-hyperconjugative delocalization. Despite a lower spin population of the ligand in sigma-hyperconjugative transmission, the hyperfine couplings can be larger because of the direct involvement of the ligand s-orbitals in this delocalization pathway. We demonstrate a quantitative correlation between the hyperfine couplings of aromatic ligand atoms and the characteristics of the metal-ligand bond modulated by the trans substituent, a hyperfine trans effect.
Czech name
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Czech description
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Classification
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
10400 - Chemical sciences
Result continuities
Project
<a href="/en/project/GA21-06991S" target="_blank" >GA21-06991S: Relativistic Effects in Paramagnetic NMR Spectroscopy</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
63
Issue of the periodical within the volume
19
Country of publishing house
US - UNITED STATES
Number of pages
13
Pages from-to
8580-8592
UT code for WoS article
001227850700001
EID of the result in the Scopus database
2-s2.0-85193102505