Nature of NMR Shifts in Paramagnetic Octahedral Ru(III)
Complexes with Axial Pyridine-Based Ligands

J 2023

Nature of NMR Shifts in Paramagnetic Octahedral Ru(III) Complexes with Axial Pyridine-Based Ligands

CHYBA, Jan; Anna HRUZÍKOVÁ; Michal KNOR; Petra PIKULOVÁ; Kateřina MARKOVÁ et al.

Základní údaje

Originální název

Nature of NMR Shifts in Paramagnetic Octahedral Ru(III) Complexes with Axial Pyridine-Based Ligands

Autoři

CHYBA, Jan ; Anna HRUZÍKOVÁ; Michal KNOR; Petra PIKULOVÁ; Kateřina MARKOVÁ; Jan NOVOTNÝ a Radek MAREK

Vydání

Inorganic Chemistry, American Chemical Society, 2023, 0020-1669

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10400 1.4 Chemical sciences

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/acs.inorgchem.2c03282

Impakt faktor

Impact factor: 4.300

Kód RIV

RIV/00216224:14740/23:00130308

Organizační jednotka

Středoevropský technologický institut

DOI

https://doi.org/10.1021/acs.inorgchem.2c03282

UT WoS

000935442300001

EID Scopus

2-s2.0-85148004658

Klíčová slova anglicky

NMR spectroscopy;hyperfine interaction;ruthenium(III);relativistic DFT;stability

Štítky

14313010, CF BIC, CF NMR, CF PROT, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 17. 10. 2024 12:32, Ing. Marie Švancarová

Anotace

V originále

In recent decades, transition-metal coordination compounds have been extensively studied for their antitumor and antimetastatic activities. In this work, we synthesized a set of symmetric and asymmetric Ru(III) and Rh(III) coordination compounds of the general structure (Na+/K+/PPh4+/LH+) [trans-M(III)L(eq)nL(ax)2]- (M = Ru(III) or Rh(III); L(eq) = Cl, n = 4; L(eq) = ox, n = 2; L(ax) = 4-R-pyridine, R = CH3, H, C6H5, COOH, CF3, CN; L(ax) = DMSO-S) and systematically investigated their structure, stability, and NMR properties. 1H and 13C NMR spectra measured at various temperatures were used to break down the total NMR shifts into the orbital (temperature independent) and hyperfine (temperature dependent) contributions. The hyperfine NMR shifts for paramagnetic Ru(III) compounds were analyzed in detail by using relativistic density-functional theory (DFT). The effects of i) the 4-R substituent of pyridine, ii) the axial trans ligand L(ax), and iii) the equatorial ligands L(eq) on the distribution of spin density reflected in the “through-bond” (contact) and the “through-space” (pseudocontact) contributions to the hyperfine NMR shifts of the individual atoms of the pyridine ligands are rationalized. Further, we demonstrate the large effects of the solvent on the hyperfine NMR shifts and discuss our observations in the general context of the paramagnetic NMR spectroscopy of transition-metal complexes.

Návaznosti

EF18_046/0015974, projekt VaV

Název: Modernizace České infrastruktury pro integrativní strukturní biologii

GA21-06991S, projekt VaV

Název: Relativistické efekty v paramagnetické NMR spektroskopii (Akronym: RELMAG)

Investor: Grantová agentura ČR, Relativistické efekty v paramagnetické NMR spektroskopii

MUNI/C/0107/2022, interní kód MU

Název: Výpočty NMR a EPR parametrů pomocí nástrojů relativistické kvantové chemie

Investor: Masarykova univerzita, Výpočty NMR a EPR parametrů pomocí nástrojů relativistické kvantové chemie, Podpora vynikajících diplomových prací

90127, velká výzkumná infrastruktura

Název: CIISB II

90140, velká výzkumná infrastruktura

Název: e-INFRA CZ

Přiložené soubory

IC23_62_3381_acs.inorgchem.2c03282.pdf

Požádat o autorskou verzi souboru

Citovat

CHYBA, Jan; Anna HRUZÍKOVÁ; Michal KNOR; Petra PIKULOVÁ; Kateřina MARKOVÁ; Jan NOVOTNÝ a Radek MAREK. Nature of NMR Shifts in Paramagnetic Octahedral Ru(III) Complexes with Axial Pyridine-Based Ligands. Inorganic Chemistry. American Chemical Society, 2023, roč. 62, č. 8, s. 3381-3394. ISSN 0020-1669. Dostupné z: https://doi.org/10.1021/acs.inorgchem.2c03282.

@article{2254007,
   author = {Chyba, Jan and Hruzíková, Anna and Knor, Michal and Pikulová, Petra and Marková, Kateřina and Novotný, Jan and Marek, Radek},
   article_number = {8},
   doi = {https://doi.org/10.1021/acs.inorgchem.2c03282},
   keywords = {NMR spectroscopy;hyperfine interaction;ruthenium(III);relativistic DFT;stability},
   language = {eng},
   issn = {0020-1669},
   journal = {Inorganic Chemistry},
   title = {Nature of NMR Shifts in Paramagnetic Octahedral Ru(III) Complexes with Axial Pyridine-Based Ligands},
   url = {http://dx.doi.org/10.1021/acs.inorgchem.2c03282},
   volume = {62},
   year = {2023}
}

TY  - JOUR
ID  - 2254007
AU  - Chyba, Jan - Hruzíková, Anna - Knor, Michal - Pikulová, Petra - Marková, Kateřina - Novotný, Jan - Marek, Radek
PY  - 2023
TI  - Nature of NMR Shifts in Paramagnetic Octahedral Ru(III) Complexes with Axial Pyridine-Based Ligands
JF  - Inorganic Chemistry
VL  - 62
IS  - 8
SP  - 3381-3394
EP  - 3381-3394
PB  - American Chemical Society
SN  - 00201669
KW  - NMR spectroscopy;hyperfine interaction;ruthenium(III);relativistic DFT;stability
UR  - http://dx.doi.org/10.1021/acs.inorgchem.2c03282
N2  - In recent decades, transition-metal coordination compounds have been extensively studied for their antitumor and antimetastatic activities. In this work, we synthesized a set of symmetric and asymmetric Ru(III) and Rh(III) coordination compounds of the general structure (Na+/K+/PPh4+/LH+) [trans-M(III)L(eq)nL(ax)2]- (M = Ru(III) or Rh(III); L(eq) = Cl, n = 4; L(eq) = ox, n = 2; L(ax) = 4-R-pyridine, R = CH3, H, C6H5, COOH, CF3, CN; L(ax) = DMSO-S) and systematically investigated their structure, stability, and NMR properties. 1H and 13C NMR spectra measured at various temperatures were used to break down the total NMR shifts into the orbital (temperature independent) and hyperfine (temperature dependent) contributions. The hyperfine NMR shifts for paramagnetic Ru(III) compounds were analyzed in detail by using relativistic density-functional theory (DFT). The effects of i) the 4-R substituent of pyridine, ii) the axial trans ligand L(ax), and iii) the equatorial ligands L(eq) on the distribution of spin density reflected in the “through-bond” (contact) and the “through-space” (pseudocontact) contributions to the hyperfine NMR shifts of the individual atoms of the pyridine ligands are rationalized. Further, we demonstrate the large effects of the solvent on the hyperfine NMR shifts and discuss our observations in the general context of the paramagnetic NMR spectroscopy of transition-metal complexes.
ER  -

CHYBA, Jan; Anna HRUZÍKOVÁ; Michal KNOR; Petra PIKULOVÁ; Kateřina MARKOVÁ; Jan NOVOTNÝ a Radek MAREK. Nature of NMR Shifts in Paramagnetic Octahedral Ru(III) Complexes with Axial Pyridine-Based Ligands. \textit{Inorganic Chemistry}. American Chemical Society, 2023, roč.~62, č.~8, s.~3381-3394. ISSN~0020-1669. Dostupné z: https://doi.org/10.1021/acs.inorgchem.2c03282.

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