Determination of the orbital and paramagnetic contributions to
the 1H and 13C NMR chemical shifts of ruthenium(III) complexes

k 2017

Determination of the orbital and paramagnetic contributions to the 1H and 13C NMR chemical shifts of ruthenium(III) complexes

JEREMIAS, Lukáš, Jan NOVOTNÝ, Michal REPISKY, Stanislav KOMOROVSKY, Radek MAREK et. al.

Základní údaje

Originální název

Determination of the orbital and paramagnetic contributions to the 1H and 13C NMR chemical shifts of ruthenium(III) complexes

Autoři

JEREMIAS, Lukáš (203 Česká republika, domácí), Jan NOVOTNÝ (203 Česká republika, domácí), Michal REPISKY (703 Slovensko), Stanislav KOMOROVSKY (703 Slovensko) a Radek MAREK (203 Česká republika, garant, domácí)

Vydání

32nd NMR Valtice - Central European NMR Meeting, 2017

Další údaje

Jazyk

angličtina

Typ výsledku

Prezentace na konferencích

Obor

10402 Inorganic and nuclear chemistry

Stát vydavatele

Česká republika

Utajení

není předmětem státního či obchodního tajemství

Kód RIV

RIV/00216224:14740/17:00095291

Organizační jednotka

Středoevropský technologický institut

Klíčová slova anglicky

pNMR; rutenium(III); DFT

Štítky

rivok

Změněno: 31. 12. 2017 10:07, RNDr. Lukáš Jeremias, Ph.D.

Anotace

V originále

The paramagnetic NMR (pNMR) spectroscopy is becoming crucially important in many areas of research despite the fact that unpaired electrons affect the NMR chemical-shift tensors, the isotropic NMR chemical shifts, and indirect nuclear spin-spin coupling constants [1]. Therefore the resonance frequencies for paramagnetic species lie typically out of the standard chemical-shift ranges for their diamagnetic analogs and the NMR signals are significantly broadened. The observed total NMR chemical shift can be decomposed into temperature-independent orbital term and temperature-dependent paramagnetic term [2]. In this study, the orbital and paramagnetic contributions to the NMR chemical shifts were determined experimentally from the 1H and 13C NMR measurements at various temperatures for a series of ruthenium(III) complexes - Ru(X-acac)3 and Ru(dbm)3 (X = H, Br, Me, NO2; acac = acetylacetonate; dbmH = dibenzoylmethane). The relativistic DFT calculations (two-component SO-ZORA and four-component DKS) were performed to assist with the resonance assignments. [1] J. Autschbach, In D. A. Dixon, Annual Reports in Computational Chemistry, Elsevier, 2015, 11, 3–36. [2] J. Novotný, M. Sojka, S. Komorovsky, M. Nečas, R. Marek, J. Am. Chem. Soc., 2016, 138, 8432–8445.

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

LM2015085, projekt VaV

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

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

Citovat

JEREMIAS, Lukáš, Jan NOVOTNÝ, Michal REPISKY, Stanislav KOMOROVSKY a Radek MAREK. Determination of the orbital and paramagnetic contributions to the 1H and 13C NMR chemical shifts of ruthenium(III) complexes. In 32nd NMR Valtice - Central European NMR Meeting. 2017.

@proceedings{1400712,
   author = {Jeremias, Lukáš and Novotný, Jan and Repisky, Michal and Komorovsky, Stanislav and Marek, Radek},
   booktitle = {32nd NMR Valtice - Central European NMR Meeting},
   keywords = {pNMR; rutenium(III); DFT},
   language = {eng},
   title = {Determination of the orbital and paramagnetic contributions to the 1H and 13C NMR chemical shifts of ruthenium(III) complexes},
   year = {2017}
}

TY  - CONF
ID  - 1400712
AU  - Jeremias, Lukáš - Novotný, Jan - Repisky, Michal - Komorovsky, Stanislav - Marek, Radek
PY  - 2017
TI  - Determination of the orbital and paramagnetic contributions to the 1H and 13C NMR chemical shifts of ruthenium(III) complexes
KW  - pNMR
KW  - rutenium(III)
KW  - DFT
N2  - The paramagnetic NMR (pNMR) spectroscopy is becoming crucially important in many areas of research despite the fact that unpaired electrons affect the NMR chemical-shift tensors, the isotropic NMR chemical shifts, and indirect nuclear spin-spin coupling constants [1]. Therefore the resonance frequencies for paramagnetic species lie typically out of the standard chemical-shift ranges for their diamagnetic analogs and the NMR signals are significantly broadened. The observed total NMR chemical shift can be decomposed into temperature-independent orbital term and temperature-dependent paramagnetic term [2]. In this study, the orbital and paramagnetic contributions to the NMR chemical shifts were determined experimentally from the 1H and 13C NMR measurements at various temperatures for a series of ruthenium(III) complexes - Ru(X-acac)3 and Ru(dbm)3 (X = H, Br, Me, NO2; acac = acetylacetonate; dbmH = dibenzoylmethane). The relativistic DFT calculations (two-component SO-ZORA and four-component DKS) were performed to assist with the resonance assignments. [1] J. Autschbach, In D. A. Dixon, Annual Reports in Computational Chemistry, Elsevier, 2015, 11, 3–36. [2] J. Novotný, M. Sojka, S. Komorovsky, M. Nečas, R. Marek, J. Am. Chem. Soc., 2016, 138, 8432–8445.
ER  -

JEREMIAS, Lukáš, Jan NOVOTNÝ, Michal REPISKY, Stanislav KOMOROVSKY a Radek MAREK. Determination of the orbital and paramagnetic contributions to the 1H and 13C NMR chemical shifts of ruthenium(III) complexes. In \textit{32nd NMR Valtice - Central European NMR Meeting}. 2017.

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