Mechanisms of Ligand Hyperfine Coupling in Transition-Metal
Complexes: σ and π Transmission Pathways

J 2024

Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways

NOVOTNÝ, Jan, Markéta MUNZAROVÁ a Radek MAREK

Základní údaje

Originální název

Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways

Autoři

NOVOTNÝ, Jan (203 Česká republika, domácí), Markéta MUNZAROVÁ (203 Česká republika, domácí) a Radek MAREK (203 Česká republika, garant, domácí)

Vydání

Inorganic Chemistry, American Chemical Society, 2024, 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.3c04425

Impakt faktor

Impact factor: 4.600 v roce 2022

Organizační jednotka

Přírodovědecká fakulta

DOI

http://dx.doi.org/10.1021/acs.inorgchem.3c04425

Klíčová slova anglicky

EPR;pNMR;hyperfine interaction;Fermi contact;pi-conjugation;sigma-hyperconjugation

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 27. 5. 2024 15:33, prof. RNDr. Radek Marek, Ph.D.

Anotace

V originále

Theoretical interpretation of hyperfine interactions was pioneered in the 1950s-1960s by the seminal works of McConnell, Karplus, and others for organic radicals and by Watson and Freeman for transition-metal (TM) complexes. In this work, we investigate a series of octahedral Ru(III) complexes with aromatic ligands to understand the mechanism of transmission of the spin density from the d-orbital of the metal to the s-orbitals of the ligand atoms. Spin densities and spin populations underlying ligand hyperfine couplings are analyzed in terms of pi-conjugative or sigma-hyperconjugative delocalization vs. spin polarization based on symmetry considerations and restricted open-shell vs. unrestricted wave function analysis. The transmission of spin density is shown to be most efficient in the case of symmetry-allowed pi-conjugative delocalization, but when the pi-conjugation is partially or fully symmetry-forbidden, it can be surpassed by the sigma-hyperconjugative delocalization. Despite a lower spin population of the ligand in sigma-hyperconjugative transmission, the hyperfine couplings can be larger because of the direct involvement of the ligand s-orbitals in this delocalization pathway. We demonstrate a quantitative correlation between the hyperfine couplings of aromatic ligand atoms and the characteristics of the metal-ligand bond modulated by the trans substituent, a hyperfine trans effect.

Návaznosti

GA21-06991S, projekt VaV

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

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

90140, velká výzkumná infrastruktura

Název: e-INFRA CZ

Přiložené soubory

IC24_63_8580_acs.inorgchem.3c04424.pdf

Požádat o autorskou verzi souboru

Citovat

NOVOTNÝ, Jan, Markéta MUNZAROVÁ a Radek MAREK. Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways. Inorganic Chemistry. American Chemical Society, 2024, roč. 63, č. 19, s. 8580-8592. ISSN 0020-1669. Dostupné z: https://dx.doi.org/10.1021/acs.inorgchem.3c04425.

@article{2399546,
   author = {Novotný, Jan and Munzarová, Markéta and Marek, Radek},
   article_number = {19},
   doi = {http://dx.doi.org/10.1021/acs.inorgchem.3c04425},
   keywords = {EPR;pNMR;hyperfine interaction;Fermi contact;pi-conjugation;sigma-hyperconjugation},
   language = {eng},
   issn = {0020-1669},
   journal = {Inorganic Chemistry},
   title = {Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways},
   url = {https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04425},
   volume = {63},
   year = {2024}
}

TY  - JOUR
ID  - 2399546
AU  - Novotný, Jan - Munzarová, Markéta - Marek, Radek
PY  - 2024
TI  - Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways
JF  - Inorganic Chemistry
VL  - 63
IS  - 19
SP  - 8580-8592
EP  - 8580-8592
PB  - American Chemical Society
SN  - 00201669
KW  - EPR;pNMR;hyperfine interaction;Fermi contact;pi-conjugation;sigma-hyperconjugation
UR  - https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04425
N2  - Theoretical interpretation of hyperfine interactions was pioneered in the 1950s-1960s by the seminal works of McConnell, Karplus, and others for organic radicals and by Watson and Freeman for transition-metal (TM) complexes. In this work, we investigate a series of octahedral Ru(III) complexes with aromatic ligands to understand the mechanism of transmission of the spin density from the d-orbital of the metal to the s-orbitals of the ligand atoms. Spin densities and spin populations underlying ligand hyperfine couplings are analyzed in terms of pi-conjugative or sigma-hyperconjugative delocalization vs. spin polarization based on symmetry considerations and restricted open-shell vs. unrestricted wave function analysis. The transmission of spin density is shown to be most efficient in the case of symmetry-allowed pi-conjugative delocalization, but when the pi-conjugation is partially or fully symmetry-forbidden, it can be surpassed by the sigma-hyperconjugative delocalization. Despite a lower spin population of the ligand in sigma-hyperconjugative transmission, the hyperfine couplings can be larger because of the direct involvement of the ligand s-orbitals in this delocalization pathway. We demonstrate a quantitative correlation between the hyperfine couplings of aromatic ligand atoms and the characteristics of the metal-ligand bond modulated by the trans substituent, a hyperfine trans effect.
ER  -

NOVOTNÝ, Jan, Markéta MUNZAROVÁ a Radek MAREK. Mechanisms of Ligand Hyperfine Coupling in Transition-Metal Complexes: σ and π Transmission Pathways. \textit{Inorganic Chemistry}. American Chemical Society, 2024, roč.~63, č.~19, s.~8580-8592. ISSN~0020-1669. Dostupné z: https://dx.doi.org/10.1021/acs.inorgchem.3c04425.

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