Hyperfine Effects in Ligand NMR: Paramagnetic Ru(III) Complexes
with 3-Substituted Pyridines

J 2018

Hyperfine Effects in Ligand NMR: Paramagnetic Ru(III) Complexes with 3-Substituted Pyridines

NOVOTNÝ, Jan; David PŘICHYSTAL; Martin SOJKA; Stanislav KOMOROVSKY; Marek NEČAS et. al.

Základní údaje

Originální název

Hyperfine Effects in Ligand NMR: Paramagnetic Ru(III) Complexes with 3-Substituted Pyridines

Autoři

NOVOTNÝ, Jan; David PŘICHYSTAL; Martin SOJKA; Stanislav KOMOROVSKY; Marek NEČAS a Radek MAREK

Vydání

Inorganic Chemistry, Washington, American Chemical Society, 2018, 0020-1669

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10402 Inorganic and nuclear chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/acs.inorgchem.7b02440

Impakt faktor

Impact factor: 4.850

Kód RIV

RIV/00216224:14740/18:00100759

Organizační jednotka

Středoevropský technologický institut

DOI

https://doi.org/10.1021/acs.inorgchem.7b02440

UT WoS

000422810900015

EID Scopus

2-s2.0-85040635171

Klíčová slova anglicky

NMR spectroscopy; paramagnetic NMR; hyperfine coupling; spin density; Fermi-contact; spin-dipole; paramagnetic spin-orbit

Štítky

CF NMR, CF SAXS, rivok

Příznaky

Recenzováno

Změněno: 5. 3. 2019 09:32, Mgr. Pavla Foltynová, Ph.D.

Anotace

V originále

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.

Návaznosti

GA15-09381S, projekt VaV

Název: Struktura a vlastnosti paramagnetických komplexů ruthenia pro návrh nových protirakovinných léčiv (Akronym: PARAMAG)

Investor: Grantová agentura ČR, Struktura a vlastnosti paramagnetických komplexů ruthenia pro návrh nových protirakovinných léčiv

LM2015043, projekt VaV

Název: Česká infrastruktura pro integrativní strukturní biologii (Akronym: CIISB)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Czech Infrastructure for Integrative Structural Biology

LM2015085, projekt VaV

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

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

LQ1601, projekt VaV

Název: CEITEC 2020 (Akronym: CEITEC2020)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, CEITEC 2020

Přiložené soubory

IC18_57_641.pdf

Požádat o autorskou verzi souboru

Citovat

NOVOTNÝ, Jan; David PŘICHYSTAL; Martin SOJKA; Stanislav KOMOROVSKY; Marek NEČAS a Radek MAREK. Hyperfine Effects in Ligand NMR: Paramagnetic Ru(III) Complexes with 3-Substituted Pyridines. Inorganic Chemistry. Washington: American Chemical Society, 2018, roč. 57, č. 2, s. 641-652. ISSN 0020-1669. Dostupné z: https://doi.org/10.1021/acs.inorgchem.7b02440.

@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 = {https://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 a Radek MAREK. Hyperfine Effects in Ligand NMR: Paramagnetic Ru(III) Complexes with 3-Substituted Pyridines. \textit{Inorganic Chemistry}. Washington: American Chemical Society, 2018, roč.~57, č.~2, s.~641-652. ISSN~0020-1669. Dostupné z: https://doi.org/10.1021/acs.inorgchem.7b02440.

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