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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 (15)N and (59)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 calculat...

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Autores principales: Samultsev, Dmitry O., Semenov, Valentin A., Rusakova, Irina L., Krivdin, Leonid B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9658221/
https://www.ncbi.nlm.nih.gov/pubmed/36361968
http://dx.doi.org/10.3390/ijms232113178
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author Samultsev, Dmitry O.
Semenov, Valentin A.
Rusakova, Irina L.
Krivdin, Leonid B.
author_facet Samultsev, Dmitry O.
Semenov, Valentin A.
Rusakova, Irina L.
Krivdin, Leonid B.
author_sort Samultsev, Dmitry O.
collection PubMed
description Both four-component relativistic and nonrelativistic computations within the GIAO-DFT(PBE0) formalism have been carried out for (15)N and (59)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 (15)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.
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spelling pubmed-96582212022-11-15 Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt Samultsev, Dmitry O. Semenov, Valentin A. Rusakova, Irina L. Krivdin, Leonid B. Int J Mol Sci Article Both four-component relativistic and nonrelativistic computations within the GIAO-DFT(PBE0) formalism have been carried out for (15)N and (59)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 (15)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. MDPI 2022-10-29 /pmc/articles/PMC9658221/ /pubmed/36361968 http://dx.doi.org/10.3390/ijms232113178 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Samultsev, Dmitry O.
Semenov, Valentin A.
Rusakova, Irina L.
Krivdin, Leonid B.
Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: 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 Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9658221/
https://www.ncbi.nlm.nih.gov/pubmed/36361968
http://dx.doi.org/10.3390/ijms232113178
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