dc.contributor.author | Novotný, Jan | |
dc.contributor.author | Sojka, Martin | |
dc.contributor.author | Komorovsky, Stanislav | |
dc.contributor.author | Nečas, Marek | |
dc.contributor.author | Marek, Radek | |
dc.date.accessioned | 2017-03-15T13:46:11Z | |
dc.date.available | 2017-03-15T13:46:11Z | |
dc.date.issued | 2016-06-16 | |
dc.description.abstract | 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]+
<i>trans</i>-[Ru<sup>III</sup>Cl<sub>4</sub>(DMSO)(4-R-py)]<sup>−</sup>, 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 <sup>1</sup>H and <sup>13</sup>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<sup>orb</sup>, temperature-independent) and paramagnetic (δ<sup>para</sup>, temperature-dependent) contributions to the total NMR chemical shifts, a relativistic twocomponent DFT approach was used. The paramagnetic contributions to the <sup>13</sup>C NMR chemical shifts are correlated with the
distribution of spin density in the ligand moiety and the <sup>13</sup>C isotropic hyperfine coupling constants, A<sub>iso</sub> (<sup>13</sup>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<sup>para</sup>, 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. | en_US |
dc.description | Source:<a href=http://pubs.acs.org/doi/pdf/10.1021/jacs.6b02749>DOI:
10.1021/jacs.6b02749</a> | en_US |
dc.identifier.citation | Novotný J, Sojka, Komorovsky S, Nečas, Marek R. Interpreting the paramagnetic NMR spectra of potential Ru(III) metallodrugs: synergy between experiment and relativistic DFT calculations. Journal of the American Chemical Society. 2016;138(27):8432-8445 | en_US |
dc.identifier.cristinID | FRIDAID 1419471 | |
dc.identifier.doi | 10.1021/jacs.6b02749 | |
dc.identifier.issn | 0002-7863 | |
dc.identifier.issn | 1520-5126 | |
dc.identifier.uri | https://hdl.handle.net/10037/10708 | |
dc.language.iso | eng | en_US |
dc.publisher | American Chemical Society. Journal of the American Chemical Society | en_US |
dc.relation.journal | Journal of the American Chemical Society | |
dc.relation.projectID | Norges forskningsråd: 179568 | en_US |
dc.relation.projectID | Norges forskningsråd: 214095 | en_US |
dc.rights.accessRights | openAccess | en_US |
dc.subject | VDP::Matematikk og Naturvitenskap: 400 | en_US |
dc.title | Interpreting the paramagnetic NMR spectra of potential Ru(III) metallodrugs: synergy between experiment and relativistic DFT calculations | en_US |
dc.type | Journal article | en_US |
dc.type | Tidsskriftartikkel | en_US |
dc.type | Peer reviewed | en_US |