Unraveling the coordination isomerism by ligand hyperfine NMR
shifts

J 2026

Unraveling the coordination isomerism by ligand hyperfine NMR shifts

CIDLINSKÁ, Dora; Jan CHYBA; Markéta MUNZAROVÁ; Yevgen YURENKO; Jan NOVOTNÝ et al.

Základní údaje

Originální název

Unraveling the coordination isomerism by ligand hyperfine NMR shifts

Autoři

CIDLINSKÁ, Dora; Jan CHYBA ; Markéta MUNZAROVÁ; Yevgen YURENKO; Jan NOVOTNÝ a Radek MAREK

Vydání

Chemical Science, ROYAL SOC CHEMISTRY, 2026, 2041-6520

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10400 1.4 Chemical sciences

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1039/D5SC09905F

Impakt faktor

Impact factor: 7.400 v roce 2024

Označené pro přenos do RIV

Ano

Organizační jednotka

Středoevropský technologický institut

DOI

https://doi.org/10.1039/D5SC09905F

Klíčová slova anglicky

NMR spectroscopy; hyperfine shift; DFT calculations; spin density; Ru(III) complex; metal coordination

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 5. 3. 2026 08:01, prof. RNDr. Radek Marek, Ph.D.

Anotace

V originále

The hyperfine (Curie) NMR shifts of ligand atoms in the open-shell coordination compound report subtle details of the spin distribution around the central metal atom. In this work, we propose hyperfine NMR shifts as simple and extremely sensitive indicators of the ligand coordination geometry. This is demonstrated for equatorial versus axial isomers of neutral octahedral [Ru(acac)Cl2L2] compounds, and rationalized by two distinct mechanisms of transmission of the spin density unraveled using density-functional theory analysis. The positional interchange of the two chlorides and the two pnictogen-based ligands (L) induces modifications in the singly occupied molecular orbital composition and the related Fermi-contact hyperfine interactions of the probed atoms of the acac ligand, resulting in distinct 1H and 13C NMR spectral fingerprints. The demonstrated symmetry-driven spin-transmission mechanisms have general validity, which offers hyperfine NMR shift as a tool to probe the geometry of various classes of coordination compounds, including transition-metal catalysts and metalloenzymes.

Návaznosti

GA24-10760S, projekt VaV

Název: Relativistické spin-orbitální efekty v molekulární struktuře a NMR spektroskopii

Investor: Grantová agentura ČR, Relativistické spin-orbitální efekty v molekulární struktuře a NMR spektroskopii

Citovat

CIDLINSKÁ, Dora; Jan CHYBA; Markéta MUNZAROVÁ; Yevgen YURENKO; Jan NOVOTNÝ a Radek MAREK. Unraveling the coordination isomerism by ligand hyperfine NMR shifts. Chemical Science. ROYAL SOC CHEMISTRY, 2026, roč. 17, č. 12, s. 10000-10006. ISSN 2041-6520. Dostupné z: https://doi.org/10.1039/D5SC09905F.

@article{2558417,
   author = {Cidlinská, Dora and Chyba, Jan and Munzarová, Markéta and Yurenko, Yevgen and Novotný, Jan and Marek, Radek},
   article_number = {12},
   doi = {https://doi.org/10.1039/D5SC09905F},
   keywords = {NMR spectroscopy; hyperfine shift; DFT calculations; spin density; Ru(III) complex; metal coordination},
   language = {eng},
   issn = {2041-6520},
   journal = {Chemical Science},
   title = {Unraveling the coordination isomerism by ligand hyperfine NMR shifts},
   url = {https://doi.org/10.1039/D5SC09905F},
   volume = {17},
   year = {2026}
}

TY  - JOUR
ID  - 2558417
AU  - Cidlinská, Dora - Chyba, Jan - Munzarová, Markéta - Yurenko, Yevgen - Novotný, Jan - Marek, Radek
PY  - 2026
TI  - Unraveling the coordination isomerism by ligand hyperfine NMR shifts
JF  - Chemical Science
VL  - 17
IS  - 12
SP  - 10000-10006
EP  - 10000-10006
PB  - ROYAL SOC CHEMISTRY
SN  - 20416520
KW  - NMR spectroscopy
KW  - hyperfine shift
KW  - DFT calculations
KW  - spin density
KW  - Ru(III) complex
KW  - metal coordination
UR  - https://doi.org/10.1039/D5SC09905F
N2  - The hyperfine (Curie) NMR shifts of ligand atoms in the open-shell coordination compound report subtle details of the spin distribution around the central metal atom. In this work, we propose hyperfine NMR shifts as simple and extremely sensitive indicators of the ligand coordination geometry. This is demonstrated for equatorial versus axial isomers of neutral octahedral [Ru(acac)Cl2L2] compounds, and rationalized by two distinct mechanisms of transmission of the spin density unraveled using density-functional theory analysis. The positional interchange of the two chlorides and the two pnictogen-based ligands (L) induces modifications in the singly occupied molecular orbital composition and the related Fermi-contact hyperfine interactions of the probed atoms of the acac ligand, resulting in distinct 1H and 13C NMR spectral fingerprints. The demonstrated symmetry-driven spin-transmission mechanisms have general validity, which offers hyperfine NMR shift as a tool to probe the geometry of various classes of coordination compounds, including transition-metal catalysts and metalloenzymes.
ER  -

CIDLINSKÁ, Dora; Jan CHYBA; Markéta MUNZAROVÁ; Yevgen YURENKO; Jan NOVOTNÝ a Radek MAREK. Unraveling the coordination isomerism by ligand hyperfine NMR shifts. \textit{Chemical Science}. ROYAL SOC CHEMISTRY, 2026, roč.~17, č.~12, s.~10000-10006. ISSN~2041-6520. Dostupné z: https://doi.org/10.1039/D5SC09905F.

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