Structure, solvent, and relativistic effects on the NMR
chemical shifts in square-planar transition-metal complexes:
assessment of DFT approaches

J 2015

Structure, solvent, and relativistic effects on the NMR chemical shifts in square-planar transition-metal complexes: assessment of DFT approaches

VÍCHA, Jan; Jan NOVOTNÝ; Michal STRAKA; Michal REPISKY; Kenneth RUUD et al.

Základní údaje

Originální název

Structure, solvent, and relativistic effects on the NMR chemical shifts in square-planar transition-metal complexes: assessment of DFT approaches

Autoři

VÍCHA, Jan; Jan NOVOTNÝ; Michal STRAKA; Michal REPISKY; Kenneth RUUD; Stanislav KOMOROVSKY a Radek MAREK

Vydání

Physical Chemistry Chemical Physics, Cambridge, Royal Society of Chemistry, 2015, 1463-9076

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1039/C5CP04214C

Impakt faktor

Impact factor: 4.449

Označené pro přenos do RIV

Ano

Kód RIV

RIV/00216224:14740/15:00080968

Organizační jednotka

Středoevropský technologický institut

DOI

https://doi.org/10.1039/C5CP04214C

UT WoS

000361697400043

EID Scopus

2-s2.0-84942455846

Klíčová slova anglicky

Transition-metal complex; geometry; NMR chemical shift; relativistic DFT; gold; platinum

Štítky

podil

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 3. 9. 2016 18:14, prof. RNDr. Radek Marek, Ph.D.

Anotace

V originále

The role of various factors (structure, solvent, and relativistic treatment) was evaluated for square-planar 4d and 5d transition-metal complexes. The DFT approach for calculating the structures was calibrated using a cluster approach and compared to X-ray geometries, with the PBE0 functional (def2-TZVPP basis set) providing the best results, followed closely by the hybrid TPSSH and the MN12SX functional. Calculations of the NMR chemical shifts using the two-component (2c, Zeroth-Order Regular Approximation as implemented in ADF package) and four-component (4c, Dirac-Coulomb as implemented in ReSpect code) relativistic approaches were performed to analyze and demonstrate the importance of solvent corrections (2c) as well as a proper treatment of relativistic effects (4c). The importance of increased exact-exchange admixture in the functional (here PBE0) for reproducing the experimental data using the current implementation of the 2c approach is partly rationalized as a compensation for the missing exchange-correlation response kernel. The kernel contribution was identified to be about 15–20% of the spin-orbit-induced NMR chemical shift, DELTA(SO), which roughly corresponds to an increase in DELTA(SO) introduced by the artificially increased exact-exchange admixture in the functional. Finally, the role of individual effects (geometry, solvent, relativity) to NMR chemical shift is discussed in selected complexes. Although a fully relativistic DFT approach is still awaiting the implementation of GIAOs for hybrid functionals and an implicit solvent model, it nevertheless provides reliable NMR chemical shift data at an affordable computational cost. It is expected to outperform 2c approach, in particular for the calculation of NMR parameters in heavy element compounds.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

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

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

PCCP15_17_24944_OA.pdf

Požádat o autorskou verzi souboru

Citovat

VÍCHA, Jan; Jan NOVOTNÝ; Michal STRAKA; Michal REPISKY; Kenneth RUUD; Stanislav KOMOROVSKY a Radek MAREK. Structure, solvent, and relativistic effects on the NMR chemical shifts in square-planar transition-metal complexes: assessment of DFT approaches. Physical Chemistry Chemical Physics. Cambridge: Royal Society of Chemistry, 2015, roč. 17, č. 38, s. 24944-24955. ISSN 1463-9076. Dostupné z: https://doi.org/10.1039/C5CP04214C.

@article{1309100,
   author = {Vícha, Jan and Novotný, Jan and Straka, Michal and Repisky, Michal and Ruud, Kenneth and Komorovsky, Stanislav and Marek, Radek},
   article_location = {Cambridge},
   article_number = {38},
   doi = {https://doi.org/10.1039/C5CP04214C},
   keywords = {Transition-metal complex; geometry; NMR chemical shift; relativistic DFT; gold; platinum},
   language = {eng},
   issn = {1463-9076},
   journal = {Physical Chemistry Chemical Physics},
   title = {Structure, solvent, and relativistic effects on the NMR chemical shifts in square-planar transition-metal complexes: assessment of DFT approaches},
   url = {http://dx.doi.org/10.1039/C5CP04214C},
   volume = {17},
   year = {2015}
}

TY  - JOUR
ID  - 1309100
AU  - Vícha, Jan - Novotný, Jan - Straka, Michal - Repisky, Michal - Ruud, Kenneth - Komorovsky, Stanislav - Marek, Radek
PY  - 2015
TI  - Structure, solvent, and relativistic effects on the NMR chemical shifts in square-planar transition-metal complexes: assessment of DFT approaches
JF  - Physical Chemistry Chemical Physics
VL  - 17
IS  - 38
SP  - 24944-24955
EP  - 24944-24955
PB  - Royal Society of Chemistry
SN  - 14639076
KW  - Transition-metal complex
KW  - geometry
KW  - NMR chemical shift
KW  - relativistic DFT
KW  - gold
KW  - platinum
UR  - http://dx.doi.org/10.1039/C5CP04214C
L2  - http://dx.doi.org/10.1039/C5CP04214C
N2  - The role of various factors (structure, solvent, and relativistic treatment) was evaluated for square-planar 4d and 5d transition-metal complexes. The DFT approach for calculating the structures was calibrated using a cluster approach and compared to X-ray geometries, with the PBE0 functional (def2-TZVPP basis set) providing the best results, followed closely by the hybrid TPSSH and the MN12SX functional. Calculations of the NMR chemical shifts using the two-component (2c, Zeroth-Order Regular Approximation as implemented in ADF package) and four-component (4c, Dirac-Coulomb as implemented in ReSpect code) relativistic approaches were performed to analyze and demonstrate the importance of solvent corrections (2c) as well as a proper treatment of relativistic effects (4c). The importance of increased exact-exchange admixture in the functional (here PBE0) for reproducing the experimental data using the current implementation of the 2c approach is partly rationalized as a compensation for the missing exchange-correlation response kernel. The kernel contribution was identified to be about 15–20% of the spin-orbit-induced NMR chemical shift, DELTA(SO), which roughly corresponds to an increase in DELTA(SO) introduced by the artificially increased exact-exchange admixture in the functional. Finally, the role of individual effects (geometry, solvent, relativity) to NMR chemical shift is discussed in selected complexes. Although a fully relativistic DFT approach is still awaiting the implementation of GIAOs for hybrid functionals and an implicit solvent model, it nevertheless provides reliable NMR chemical shift data at an affordable computational cost. It is expected to outperform 2c approach, in particular for the calculation of NMR parameters in heavy element compounds.
ER  -

VÍCHA, Jan; Jan NOVOTNÝ; Michal STRAKA; Michal REPISKY; Kenneth RUUD; Stanislav KOMOROVSKY a Radek MAREK. Structure, solvent, and relativistic effects on the NMR chemical shifts in square-planar transition-metal complexes: assessment of DFT approaches. \textit{Physical Chemistry Chemical Physics}. Cambridge: Royal Society of Chemistry, 2015, roč.~17, č.~38, s.~24944-24955. ISSN~1463-9076. Dostupné z: https://doi.org/10.1039/C5CP04214C.

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