Interpreting the paramagnetic NMR spectra of potential Ru(III)
metallodrugs: Synergy between experiment and relativistic DFT
calculations

J 2016

Interpreting the paramagnetic NMR spectra of potential Ru(III) metallodrugs: Synergy between experiment and relativistic DFT calculations

NOVOTNÝ, Jan, Martin SOJKA, Stanislav KOMOROVSKY, Marek NEČAS, Radek MAREK et. al.

Základní údaje

Originální název

Interpreting the paramagnetic NMR spectra of potential Ru(III) metallodrugs: Synergy between experiment and relativistic DFT calculations

Autoři

NOVOTNÝ, Jan (203 Česká republika, domácí), Martin SOJKA (203 Česká republika, domácí), Stanislav KOMOROVSKY (703 Slovensko), Marek NEČAS (203 Česká republika, domácí) a Radek MAREK (203 Česká republika, garant, domácí)

Vydání

Journal of the American Chemical Society, Washington, American Chemical Society, 2016, 0002-7863

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/jacs.6b02749

Impakt faktor

Impact factor: 13.858

Kód RIV

RIV/00216224:14740/16:00087989

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1021/jacs.6b02749

UT WoS

000379794400026

Klíčová slova anglicky

paramagnetic NMR; ruthenium; chemical shift; contact shift; hyperfine coupling; DFT; spin density;

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 13. 3. 2018 10:18, doc. Mgr. Marek Nečas, Ph.D.

Anotace

V originále

Ruthenium-based compounds are potential candidates for use as anticancer metallodrugs. The central ruthenium atom can be in the oxidation state +2 (e.g., RAPTA, RAED) or +3 (e.g., NAMI, KP). In this study we focus on paramagnetic NAMI analogs of a general structure [4-R-pyH]+trans-[RuIIICl4(DMSO)(4-R-py)]-, where 4-R-py stands for a 4-substituted pyridine. As paramagnetic systems are generally considered difficult to characterize in detail by NMR spectroscopy, we performed a systematic structural and methodological NMR study of complexes containing variously substituted pyridines. The effect of the paramagnetic nature of these complexes on the 1H and 13C NMR chemical shifts was systematically investigated by temperature-dependent NMR experiments and density-functional theory (DFT) calculations. To understand the electronic factors influencing the orbital (delta(orb), temperature-independent) and paramagnetic (delta(para), temperature-dependent) contributions to the total NMR chemical shifts, a relativistic two-component DFT approach was used. The paramagnetic contributions to the 13C NMR chemical shifts are correlated with the distribution of spin density in the ligand moiety and the 13C isotropic hyperfine coupling constants, Aiso(13C), for the individual carbon atoms. To analyze the mechanism of spin distribution in the ligand, the contributions of molecular spin-orbitals (MSOs) to the hyperfine coupling constants and the spatial distribution of the z-component of the spin density in the MSOs calculated at the relativistic four-component DFT level are discussed and rationalized. The significant effects of the substituent and the solvent on delta(para), particularly the contact contribution, are demonstrated. This work should contribute to further understanding of the link between the electronic structure and the NMR chemical shifts in open-shell systems, including the ruthenium-based metallodrugs investigated in this account.

Návaznosti

ED3.2.00/08.0144, projekt VaV

Název: CERIT Scientific Cloud

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

LM2010005, projekt VaV

Název: Velká infrastruktura CESNET (Akronym: VI CESNET)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Velká infrastruktura CESNET

NF-CZ07-MOP-3-3492015, interní kód MU

Název: Development of Paramagnetic NMR Spectroscopy of Metallodrugs

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Development of Paramagnetic NMR Spectroscopy of Metallodrugs, Projekty mobilit a stáží

Přiložené soubory

JACS16_138_8432_6b02749.pdf

Požádat o autorskou verzi souboru

Citovat

NOVOTNÝ, Jan, Martin SOJKA, Stanislav KOMOROVSKY, Marek NEČAS a Radek MAREK. Interpreting the paramagnetic NMR spectra of potential Ru(III) metallodrugs: Synergy between experiment and relativistic DFT calculations. Journal of the American Chemical Society. Washington: American Chemical Society, 2016, roč. 138, č. 27, s. 8432-8445. ISSN 0002-7863. Dostupné z: https://dx.doi.org/10.1021/jacs.6b02749.

@article{1347774,
   author = {Novotný, Jan and Sojka, Martin and Komorovsky, Stanislav and Nečas, Marek and Marek, Radek},
   article_location = {Washington},
   article_number = {27},
   doi = {http://dx.doi.org/10.1021/jacs.6b02749},
   keywords = {paramagnetic NMR; ruthenium; chemical shift; contact shift; hyperfine coupling; DFT; spin density;},
   language = {eng},
   issn = {0002-7863},
   journal = {Journal of the American Chemical Society},
   title = {Interpreting the paramagnetic NMR spectra of potential Ru(III) metallodrugs: Synergy between experiment and relativistic DFT calculations},
   url = {http://dx.doi.org/10.1021/jacs.6b02749},
   volume = {138},
   year = {2016}
}

TY  - JOUR
ID  - 1347774
AU  - Novotný, Jan - Sojka, Martin - Komorovsky, Stanislav - Nečas, Marek - Marek, Radek
PY  - 2016
TI  - Interpreting the paramagnetic NMR spectra of potential Ru(III) metallodrugs: Synergy between experiment and relativistic DFT calculations
JF  - Journal of the American Chemical Society
VL  - 138
IS  - 27
SP  - 8432-8445
EP  - 8432-8445
PB  - American Chemical Society
SN  - 00027863
KW  - paramagnetic NMR
KW  - ruthenium
KW  - chemical shift
KW  - contact shift
KW  - hyperfine coupling
KW  - DFT
KW  - spin density;
UR  - http://dx.doi.org/10.1021/jacs.6b02749
L2  - http://dx.doi.org/10.1021/jacs.6b02749
N2  - Ruthenium-based compounds are potential candidates for use as anticancer metallodrugs. The central ruthenium atom can be in the oxidation state +2 (e.g., RAPTA, RAED) or +3 (e.g., NAMI, KP). In this study we focus on paramagnetic NAMI analogs of a general structure [4-R-pyH]+trans-[RuIIICl4(DMSO)(4-R-py)]-, where 4-R-py stands for a 4-substituted pyridine. As paramagnetic systems are generally considered difficult to characterize in detail by NMR spectroscopy, we performed a systematic structural and methodological NMR study of complexes containing variously substituted pyridines. The effect of the paramagnetic nature of these complexes on the 1H and 13C NMR chemical shifts was systematically investigated by temperature-dependent NMR experiments and density-functional theory (DFT) calculations. To understand the electronic factors influencing the orbital (delta(orb), temperature-independent) and paramagnetic (delta(para), temperature-dependent) contributions to the total NMR chemical shifts, a relativistic two-component DFT approach was used. The paramagnetic contributions to the 13C NMR chemical shifts are correlated with the distribution of spin density in the ligand moiety and the 13C isotropic hyperfine coupling constants, Aiso(13C), for the individual carbon atoms. To analyze the mechanism of spin distribution in the ligand, the contributions of molecular spin-orbitals (MSOs) to the hyperfine coupling constants and the spatial distribution of the z-component of the spin density in the MSOs calculated at the relativistic four-component DFT level are discussed and rationalized. The significant effects of the substituent and the solvent on delta(para), particularly the contact contribution, are demonstrated. This work should contribute to further understanding of the link between the electronic structure and the NMR chemical shifts in open-shell systems, including the ruthenium-based metallodrugs investigated in this account.
ER  -

NOVOTNÝ, Jan, Martin SOJKA, Stanislav KOMOROVSKY, Marek NEČAS a Radek MAREK. Interpreting the paramagnetic NMR spectra of potential Ru(III) metallodrugs: Synergy between experiment and relativistic DFT calculations. \textit{Journal of the American Chemical Society}. Washington: American Chemical Society, 2016, roč.~138, č.~27, s.~8432-8445. ISSN~0002-7863. Dostupné z: https://dx.doi.org/10.1021/jacs.6b02749.

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