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

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Publikace nespadá pod Pedagogickou fakultu, ale pod Středoevropský technologický institut. Oficiální stránka publikace je na webu muni.cz.
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JEREMIAS Lukáš NOVOTNÝ Jan REPISKY Michal KOMOROVSKY Stanislav MAREK Radek

Rok publikování 2017
Druh Další prezentace na konferencích
Fakulta / Pracoviště MU

Středoevropský technologický institut

Citace
Popis 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.
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