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@article{1397318,
author = {Novotný, Jan and Přichystal, David and Sojka, Martin and Komorovsky, Stanislav and Nečas, Marek and Marek, Radek},
article_location = {Washington},
article_number = {2},
doi = {http://dx.doi.org/10.1021/acs.inorgchem.7b02440},
keywords = {NMR spectroscopy; paramagnetic NMR; hyperfine coupling; spin density; Fermi-contact; spin-dipole; paramagnetic spin-orbit},
language = {eng},
issn = {0020-1669},
journal = {Inorganic Chemistry},
title = {Hyperfine Effects in Ligand NMR: Paramagnetic Ru(III) Complexes with 3-Substituted Pyridines},
url = {http://dx.doi.org/10.1021/acs.inorgchem.7b02440},
volume = {57},
year = {2018}
}
TY - JOUR
ID - 1397318
AU - Novotný, Jan - Přichystal, David - Sojka, Martin - Komorovsky, Stanislav - Nečas, Marek - Marek, Radek
PY - 2018
TI - Hyperfine Effects in Ligand NMR: Paramagnetic Ru(III) Complexes with 3-Substituted Pyridines
JF - Inorganic Chemistry
VL - 57
IS - 2
SP - 641-652
EP - 641-652
PB - American Chemical Society
SN - 00201669
KW - NMR spectroscopy
KW - paramagnetic NMR
KW - hyperfine coupling
KW - spin density
KW - Fermi-contact
KW - spin-dipole
KW - paramagnetic spin-orbit
UR - http://dx.doi.org/10.1021/acs.inorgchem.7b02440
L2 - http://dx.doi.org/10.1021/acs.inorgchem.7b02440
N2 - NMR spectroscopy is an indispensable tool in characterizing molecular systems, including transition-metal complexes. However, paramagnetic transition-metal complexes such as those with ruthenium in the +3 oxidation state are troublemakers because their unpaired electrons induce a fast nuclear spin relaxation that significantly broadens their NMR resonances. We recently demonstrated that the electronic and spin structures of paramagnetic Ru(III) systems can be characterized in unprecedented details by combining experimental NMR results with relativistic density-functional theory (Novotny et al. J. Am. Chem. Soc. 2016, 138, 8432). In this study we focus on paramagnetic analogs of NAMI with the general structure [3-R-pyH]+trans-[RuIIICl4(DMSO)(3-R-py)]-, where 3-R-py stands for a 3-substituted pyridine. The experimental NMR data are interpreted in terms of the contributions of hyperfine (HF) NMR shielding and the distribution of spin density calculated using relativistic DFT. The DFT computational methodology is evaluated, and the effects of substituents, environment, and relativity on the hyperfine shielding are discussed. Particular attention is paid to the analysis of the fundamental Fermi-contact (FC), spin-dipole (SD), and paramagnetic spin-orbit (PSO) terms that contribute to the hyperfine 1H and 13C NMR shifts of the individual atoms in the pyridine ligands and the spin-polarization effects in the ligand system that are linked to the character of the metal-ligand bond. The individual HF shielding terms are systematically discussed as they relate to the traditional, but somewhat mixed, contact and pseudocontact NMR contributions used extensively by experimental spectroscopists in biomolecular NMR and the development of PARACEST magnetic-resonance contrast agents.
ER -
NOVOTNÝ, Jan, David PŘICHYSTAL, Martin SOJKA, Stanislav KOMOROVSKY, Marek NEČAS and Radek MAREK. Hyperfine Effects in Ligand NMR: Paramagnetic Ru(III) Complexes with 3-Substituted Pyridines. \textit{Inorganic Chemistry}. Washington: American Chemical Society, 2018, vol.~57, No~2, p.~641-652. ISSN~0020-1669. Available from: https://dx.doi.org/10.1021/acs.inorgchem.7b02440.
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