Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes-Part 2: Nitrogen-Coordinated Complexes of Cobalt.

Content Provider	Europe PMC
Author	Samultsev, Dmitry O. Semenov, Valentin A. Rusakova, Irina L. Krivdin, Leonid B.
Editor	Alam, Todd M.
Copyright Year	2022
Abstract	Both four-component relativistic and nonrelativistic computations within the GIAO-DFT(PBE0) formalism have been carried out for 15N and 59Co 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 15N 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.
Journal	International Journal of Molecular Sciences [Int J Mol Sci]
Volume Number	23
DOI	10.3390/ijms232113178
PubMed Central reference number	PMC9658221
Issue Number	21
PubMed reference number	36361968
e-ISSN	14220067
Language	English
Publisher	Molecular Diversity Preservation International (MDPI)
Publisher Date	2022-10-29
Access Restriction	Open
Subject Keyword	four-component relativistic NMR calculations transition metal complexes nitrogen-coordinated complexes of cobalt
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry Molecular Biology Spectroscopy Catalysis Computer Science Applications Medicine Inorganic Chemistry Organic Chemistry