Interpreting the Paramagnetic NMR Spectra of Potential Ru(III) Metallodrugs: Synergy between Experiment and Relativistic DFT Calculations.
Ruthenium-based compounds are potential candidates for use as anticancer metallodrugs. The central ruthenium atom can be in the oxidation state +2 (e.g., RAPTA, RAED) or +3 (e.g., NAMI, KP). In this study we focus on paramagnetic NAMI analogs of a general structure [4-R-pyH]trans-[RuCl(DMSO)(4-R-py)...
| Publicado en: | Journal of the American Chemical Society Vol. 138; no. 27; pp. 8432 - 8446 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
7/13/2016
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=117043084&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 117043084 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 7/13/2016 vid: 138 iid: 27 pid: 997 pub: American Chemical Society artinfo: ui: 117043084 10.1021/jacs.6b02749 ppf: 8432 ppct: 14 formats: tig: atl: Interpreting the Paramagnetic NMR Spectra of Potential Ru(III) Metallodrugs: Synergy between Experiment and Relativistic DFT Calculations. aug: au: Novotný, Jan Sojka, Martin Komorovsky, Stanislav Nečas, Marek Marek, Radek affil: CEITEC − Central European Institute of Technology, Masaryk University, Kamenice 5, CZ − 62500 Brno, Czech Republic Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, CZ − 62500 Brno, Czech Republic Centre for Theoretical and Computational Chemistry, Department of Chemistry, UiT − The Arctic University of Norway, N-9037 Tromsø, Norway su: Nuclear magnetic resonance Ruthenium compounds Antineoplastic agents Density functional theory Hyperfine coupling Spatial distribution (Quantum optics) sug: subj: Nuclear magnetic resonance Ruthenium compounds Antineoplastic agents Density functional theory Hyperfine coupling Spatial distribution (Quantum optics) ab: Ruthenium-based compounds are potential candidates for use as anticancer metallodrugs. The central ruthenium atom can be in the oxidation state +2 (e.g., RAPTA, RAED) or +3 (e.g., NAMI, KP). In this study we focus on paramagnetic NAMI analogs of a general structure [4-R-pyH]trans-[RuCl(DMSO)(4-R-py)], where 4-R-py stands for a 4-substituted pyridine. As paramagnetic systems are generally considered difficult to characterize in detail by NMR spectroscopy, we performed a systematic structural and methodological NMR study of complexes containing variously substituted pyridines. The effect of the paramagnetic nature of these complexes on the H and C NMR chemical shifts was systematically investigated by temperature-dependent NMR experiments and density-functional theory (DFT) calculations. To understand the electronic factors influencing the orbital (δ, temperature-independent) and paramagnetic (δ, temperature-dependent) contributions to the total NMR chemical shifts, a relativistic two-component DFT approach was used. The paramagnetic contributions to the C NMR chemical shifts are correlated with the distribution of spin density in the ligand moiety and the C isotropic hyperfine coupling constants, A(C), for the individual carbon atoms. To analyze the mechanism of spin distribution in the ligand, the contributions of molecular spin-orbitals (MSOs) to the hyperfine coupling constants and the spatial distribution of the z-component of the spin density in the MSOs calculated at the relativistic four-component DFT level are discussed and rationalized. The significant effects of the substituent and the solvent on δ, particularly the contact contribution, are demonstrated. This work should contribute to further understanding of the link between the electronic structure and the NMR chemical shifts in open-shell systems, including the ruthenium-based metallodrugs investigated in this account. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2016 holdings: @attributes: islocal: N |
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