Další formáty:
BibTeX
LaTeX
RIS
@article{2399546,
author = {Novotný, Jan and Munzarová, Markéta and Marek, Radek},
article_number = {19},
doi = {http://dx.doi.org/10.1021/acs.inorgchem.3c04425},
keywords = {EPR;pNMR;hyperfine interaction;Fermi contact;pi-conjugation;sigma-hyperconjugation},
language = {eng},
issn = {0020-1669},
journal = {Inorganic Chemistry},
title = {Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways},
url = {https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04425},
volume = {63},
year = {2024}
}
TY - JOUR
ID - 2399546
AU - Novotný, Jan - Munzarová, Markéta - Marek, Radek
PY - 2024
TI - Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways
JF - Inorganic Chemistry
VL - 63
IS - 19
SP - 8580-8592
EP - 8580-8592
PB - American Chemical Society
SN - 00201669
KW - EPR;pNMR;hyperfine interaction;Fermi contact;pi-conjugation;sigma-hyperconjugation
UR - https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04425
N2 - 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.
ER -
NOVOTNÝ, Jan, Markéta MUNZAROVÁ a Radek MAREK. Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways. \textit{Inorganic Chemistry}. American Chemical Society, 2024, roč.~63, č.~19, s.~8580-8592. ISSN~0020-1669. Dostupné z: https://dx.doi.org/10.1021/acs.inorgchem.3c04425.
|
