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.

doi:10.3390/ijms232113178

Cited by 5 publications

(9 citation statements)

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“…The coefficient of determination (R 2 ) of 0.9966, the slope of 0.9837 ± 0.0102, and the y-intercept of 67.4421 ± 78.7321 illustrate the quality and the predictive capacity of the proposed computational protocol. Among the 34 Co(III) complexes included in the present work, six were recently studied by Samultsev et al [27] using the 4c-Rel approximation. Our calculated results show that the values predicted by Model 1 (20 ≤ AD ≤ 147 ppm) were better than those predicted in ref.…”

Section: Validation Of the Computational Protocolmentioning

confidence: 99%

“…Our calculated results show that the values predicted by Model 1 (20 ≤ AD ≤ 147 ppm) were better than those predicted in ref. [27] for all six complexes (see Table 4). Among the 34 Co(III) complexes included in the present work, six were recently studied by Samultsev et al [27] using the 4c-Rel approximation.…”

Section: Validation Of the Computational Protocolmentioning

confidence: 99%

“…[27] for all six complexes (see Table 4). Among the 34 Co(III) complexes included in the present work, six were recently studied by Samultsev et al [27] using the 4c-Rel approximation. Our calculated results show that the values predicted by Model 1 (20 ≤ AD ≤ 147 ppm) were better than those predicted in ref.…”

Section: Validation Of the Computational Protocolmentioning

confidence: 99%

“…Furthermore, the authors showed that the solvent effects on both geometry and δ 59 Co were welldescribed using the PCM (Polarizable Continuum Model) implicit model. Four-componentrelativistic (4c-Rel) calculations have been employed to calculate NMR chemical shifts in Co complexes [25][26][27][28]. Nonrelativistic (NRel) and relativistic (Rel) calculations of the NMR of light nuclei in the neighboring of metallic center were carried out by Semenov et al [25].…”

Section: Introductionmentioning

confidence: 99%

“…When the Co metal center is replaced by iridium (Ir), the variation was 67.4%, demonstrating that the Rel corrections are more important for heavier nuclei. In another study, Samultsev et al [27] calculated the δ 59 Co for a set of 27 Co complexes employing NRel and 4c-Rel approaches. The authors quantified the average contributions of relativistic and solvent effects on the calculated shielding constants as 4% and 1.4%, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Assessment of a Computational Protocol for Predicting Co-59 NMR Chemical Shift

et al. 2023

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In the present study, we benchmark computational protocols for predicting Co-59 NMR chemical shift. Quantum mechanical calculations based on density functional theory were used, in conjunction with our NMR-DKH basis sets for all atoms, including Co, which were developed in the present study. The best protocol included the geometry optimization at BLYP/def2-SVP/def2-SVP/IEF-PCM(UFF) and shielding constant calculation at GIAO-LC-ωPBE/NMR-DKH/IEF-PCM(UFF). This computational scheme was applied to a set of 34 Co(III) complexes, in which, Co-59 NMR chemical shift ranges from +1162 ppm to +15,100 ppm, and these were obtained in distinct solvents (water and organic solvents). The resulting mean absolute deviation (MAD), mean relative deviation (MRD), and coefficient of determination (R2) were 158 ppm, 3.0%, and 0.9966, respectively, suggesting an excellent alternative for studying Co-59 NMR.

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Section: Validation Of the Computational Protocolmentioning

confidence: 99%

Section: Validation Of the Computational Protocolmentioning

confidence: 99%

Section: Validation Of the Computational Protocolmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Assessment of a Computational Protocol for Predicting Co-59 NMR Chemical Shift

et al. 2023

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The Scope of the Applicability of Non‐relativistic DFT Calculations of NMR Chemical Shifts in Pyridine‐Metal Complexes for Applied Applications

Shenderovich

2024

ChemPhysChem

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Heavy metals are toxic, but it is impossible to stop using them. Considering the variety of molecular systems in which they can be present, the multicomponent nature and disorder of the structure of such systems, one of the most effective methods for studying them is NMR spectroscopy. This determines the need to calculate NMR chemical shifts for expected model systems. For elements beyond the third row of the periodic table, corrections for relativistic effects are necessary when calculating NMR parameters. Such corrections may be necessary even for light atoms due to the shielding effect of a neighboring heavy atom. This work examines the extent to which non‐relativistic DFT calculations are able to reproduce experimental 15N and 113Cd NMR chemical shift tensors in pyridine‐metal coordination complexes. It is shown that while for the calculation of 15N NMR chemical shift tensors there is no real need to consider relativistic corrections, for 113Cd, on the contrary, none of the tested calculation methods could reproduce the experimentally obtained tensor to any extent correctly.

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Theory and computation of nuclear shielding

2023

Nuclear Magnetic Resonance

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This chapter continues earlier reviews of essential works on theoretical issues of nuclear magnetic shieldings published from 1 January to 31 December 2022. As previously, the chapter concentrates on theoretical calculations of nuclear shielding parameters and/or chemical shifts in case of free molecules in the gas phase and solution, and in some cases in the solid state using a periodic formulation. The nuclear shieldings in solution are mainly calculated using inexpensive polarizable continuum model of solvent (PCM). The use of discrete solvent molecules (in particular water and other polar solvents), which is essential for correct description of hydrogen bonding, is often omitted by numerous authors. Most calculations use a relatively simple and fast, but reliable density functional theory (DFT) combined with gauge-including atomic orbital (GIAO) approach. On the other hand, reports on prediction of nuclear magnetic shielding parameters using high level theoretical methods combined with large and flexible basis sets are not so common due to the enormous computational cost. In addition, correction of raw theoretical nuclear magnetic shieldings due to ro-vibration (zero-point vibration correction, ZPVC) and temperature corrections (TC), as well as implicit and explicit solvent effects and relativistic corrections are not often reported.

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

Cited by 5 publications

References 93 publications

Assessment of a Computational Protocol for Predicting Co-59 NMR Chemical Shift

Assessment of a Computational Protocol for Predicting Co-59 NMR Chemical Shift

The Scope of the Applicability of Non‐relativistic DFT Calculations of NMR Chemical Shifts in Pyridine‐Metal Complexes for Applied Applications

Theory and computation of nuclear shielding

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