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Electron-Spin Structure and Metal-Ligand Bonding in Open-Shell Systems from Relativistic EPR and NMR: A Case Study of Square-Planar Iridium Catalysts

Identifikátory výsledku

  • Kód výsledku v IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F19%3A00107199" target="_blank" >RIV/00216224:14740/19:00107199 - isvavai.cz</a>

  • Výsledek na webu

    <a href="http://dx.doi.org/10.1021/acs.jctc.8b00914" target="_blank" >http://dx.doi.org/10.1021/acs.jctc.8b00914</a>

  • DOI - Digital Object Identifier

    <a href="http://dx.doi.org/10.1021/acs.jctc.8b00914" target="_blank" >10.1021/acs.jctc.8b00914</a>

Alternativní jazyky

  • Jazyk výsledku

    angličtina

  • Název v původním jazyce

    Electron-Spin Structure and Metal-Ligand Bonding in Open-Shell Systems from Relativistic EPR and NMR: A Case Study of Square-Planar Iridium Catalysts

  • Popis výsledku v původním jazyce

    Electron and nuclear magnetic resonance spectroscopies are indispensable and powerful methods for investigating the molecular and electronic structures of open-shell systems. We demonstrate that the NMR and EPR parameters are extremely sensitive quantitative probes for the electronic spin density around heavy-metal atoms and the metal-ligand bonding. Using relativistic density-functional theory, we have analyzed the relation between the spin density and the EPR and NMR parameters in paramagnetic iridium(II/IV) complexes with a PNP pincer ligand. As the magnetic-response parameters for compounds containing 5d transition metal(s) are heavily affected by spin-orbit coupling, relativistic effects must be included in the calculations. We have used a recent implementation of the fully-relativistic Dirac-Kohn-Sham (DKS) method employing the hybrid PBE0 functional and an implicit solvent model to calculate EPR parameters and hyperfine NMR shifts. The modulation of the metal–ligand bond by the trans substituent (-Cl or -N) and the electronic spin structure around the central metal atom and ligands are shown to be reflected in the “long-range” through-bond Fermi-contact (FC) contributions to the ligand 13C and 1H hyperfine couplings. Interestingly, the hyperfine coupling constant of the ligand atom L (A_L) bonded directly to the iridium center changes its sign because of the dominating role of the paramagnetic spin-orbit (PSO) term. Furthermore, the electronic g-shift and the PSO contribution to the ligand A_L are shown to invert their signs when nitrogen is substituted for chlorine, reflecting the different formal metal oxidation states and the change in metal–ligand bond character. A full understanding of the substituent effects is provided by using chemical bond concepts in combination with a molecular-orbital (MO) theory analysis of the second-order perturbation theory expression for the EPR parameters. Our findings are easily transferable to other systems containing d-block elements and beyond. Relativistic DFT calculations of magnetic-resonance parameters are expected to frequently assist in future experimental observations and the characterization of hitherto unknown unstable or exotic species.

  • Název v anglickém jazyce

    Electron-Spin Structure and Metal-Ligand Bonding in Open-Shell Systems from Relativistic EPR and NMR: A Case Study of Square-Planar Iridium Catalysts

  • Popis výsledku anglicky

    Electron and nuclear magnetic resonance spectroscopies are indispensable and powerful methods for investigating the molecular and electronic structures of open-shell systems. We demonstrate that the NMR and EPR parameters are extremely sensitive quantitative probes for the electronic spin density around heavy-metal atoms and the metal-ligand bonding. Using relativistic density-functional theory, we have analyzed the relation between the spin density and the EPR and NMR parameters in paramagnetic iridium(II/IV) complexes with a PNP pincer ligand. As the magnetic-response parameters for compounds containing 5d transition metal(s) are heavily affected by spin-orbit coupling, relativistic effects must be included in the calculations. We have used a recent implementation of the fully-relativistic Dirac-Kohn-Sham (DKS) method employing the hybrid PBE0 functional and an implicit solvent model to calculate EPR parameters and hyperfine NMR shifts. The modulation of the metal–ligand bond by the trans substituent (-Cl or -N) and the electronic spin structure around the central metal atom and ligands are shown to be reflected in the “long-range” through-bond Fermi-contact (FC) contributions to the ligand 13C and 1H hyperfine couplings. Interestingly, the hyperfine coupling constant of the ligand atom L (A_L) bonded directly to the iridium center changes its sign because of the dominating role of the paramagnetic spin-orbit (PSO) term. Furthermore, the electronic g-shift and the PSO contribution to the ligand A_L are shown to invert their signs when nitrogen is substituted for chlorine, reflecting the different formal metal oxidation states and the change in metal–ligand bond character. A full understanding of the substituent effects is provided by using chemical bond concepts in combination with a molecular-orbital (MO) theory analysis of the second-order perturbation theory expression for the EPR parameters. Our findings are easily transferable to other systems containing d-block elements and beyond. Relativistic DFT calculations of magnetic-resonance parameters are expected to frequently assist in future experimental observations and the characterization of hitherto unknown unstable or exotic species.

Klasifikace

  • Druh

    J<sub>imp</sub> - Článek v periodiku v databázi Web of Science

  • CEP obor

  • OECD FORD obor

    10403 - Physical chemistry

Návaznosti výsledku

  • Projekt

    Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

  • Návaznosti

    P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Ostatní

  • Rok uplatnění

    2019

  • Kód důvěrnosti údajů

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Údaje specifické pro druh výsledku

  • Název periodika

    Journal of Chemical Theory and Computation

  • ISSN

    1549-9618

  • e-ISSN

    1549-9626

  • Svazek periodika

    15

  • Číslo periodika v rámci svazku

    1

  • Stát vydavatele periodika

    US - Spojené státy americké

  • Počet stran výsledku

    14

  • Strana od-do

    201-214

  • Kód UT WoS článku

    000455558200020

  • EID výsledku v databázi Scopus

    2-s2.0-85059691868