Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt
Both four-component relativistic and nonrelativistic computations within the GIAO-DFT(PBE0) formalism have been carried out for <sup>15</sup>N and <sup>59</sup>Co NMR shielding constants and chemical shifts of a number of the nitrogen-coordinated complexes of cobalt. It was f...
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MDPI AG
2022-10-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/23/21/13178 |
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| author | Dmitry O. Samultsev Valentin A. Semenov Irina L. Rusakova Leonid B. Krivdin |
| author_facet | Dmitry O. Samultsev Valentin A. Semenov Irina L. Rusakova Leonid B. Krivdin |
| author_sort | Dmitry O. Samultsev |
| collection | DOAJ |
| description | Both four-component relativistic and nonrelativistic computations within the GIAO-DFT(PBE0) formalism have been carried out for <sup>15</sup>N and <sup>59</sup>Co NMR shielding constants and chemical shifts of a number of the nitrogen-coordinated complexes of cobalt. It was found that the total values of the calculated nitrogen chemical shifts of considered cobalt complexes span over a range of more than 580 ppm, varying from −452 to +136 ppm. At that, the relativistic corrections to nitrogen shielding constants and chemical shifts were demonstrated to be substantial, changing accordingly from ca. −19 to +74 ppm and from −68 to +25 ppm. Solvent effects on <sup>15</sup>N shielding constants and chemical shifts were shown to have contributions no less important than the relativistic effects, namely from −35 to +63 ppm and from −74 to +23 ppm, respectively. Cobalt shielding constants and chemical shifts were found to vary in the ranges of, accordingly, −20,157 to −11,373 ppm and from +3781 to +13,811. The relativistic effects are of major importance in the cobalt shielding constants, resulting in about 4% for the shielding-type contributions, while solvent corrections to cobalt shielding constants appeared to be of less significance, providing corrections of about 1.4% to the gas phase values. |
| first_indexed | 2024-03-09T19:00:38Z |
| format | Article |
| id | doaj.art-725d850674e34d16938dc1af90b6d7fd |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-09T19:00:38Z |
| publishDate | 2022-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-725d850674e34d16938dc1af90b6d7fd2023-11-24T05:03:46ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672022-10-0123211317810.3390/ijms232113178Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of CobaltDmitry O. Samultsev0Valentin A. Semenov1Irina L. Rusakova2Leonid B. Krivdin3A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, Irkutsk 664033, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, Irkutsk 664033, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, Irkutsk 664033, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, Irkutsk 664033, RussiaBoth four-component relativistic and nonrelativistic computations within the GIAO-DFT(PBE0) formalism have been carried out for <sup>15</sup>N and <sup>59</sup>Co NMR shielding constants and chemical shifts of a number of the nitrogen-coordinated complexes of cobalt. It was found that the total values of the calculated nitrogen chemical shifts of considered cobalt complexes span over a range of more than 580 ppm, varying from −452 to +136 ppm. At that, the relativistic corrections to nitrogen shielding constants and chemical shifts were demonstrated to be substantial, changing accordingly from ca. −19 to +74 ppm and from −68 to +25 ppm. Solvent effects on <sup>15</sup>N shielding constants and chemical shifts were shown to have contributions no less important than the relativistic effects, namely from −35 to +63 ppm and from −74 to +23 ppm, respectively. Cobalt shielding constants and chemical shifts were found to vary in the ranges of, accordingly, −20,157 to −11,373 ppm and from +3781 to +13,811. The relativistic effects are of major importance in the cobalt shielding constants, resulting in about 4% for the shielding-type contributions, while solvent corrections to cobalt shielding constants appeared to be of less significance, providing corrections of about 1.4% to the gas phase values.https://www.mdpi.com/1422-0067/23/21/13178four-component relativistic NMR calculationstransition metal complexesnitrogen-coordinated complexes of cobalt |
| spellingShingle | Dmitry O. Samultsev Valentin A. Semenov Irina L. Rusakova Leonid B. Krivdin Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt International Journal of Molecular Sciences four-component relativistic NMR calculations transition metal complexes nitrogen-coordinated complexes of cobalt |
| title | Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt |
| title_full | Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt |
| title_fullStr | Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt |
| title_full_unstemmed | Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt |
| title_short | Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt |
| title_sort | four component relativistic calculations of nmr shielding constants of the transition metal complexes part 2 nitrogen coordinated complexes of cobalt |
| topic | four-component relativistic NMR calculations transition metal complexes nitrogen-coordinated complexes of cobalt |
| url | https://www.mdpi.com/1422-0067/23/21/13178 |
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