Prediction of195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Tsipis, Athanassios C.; Karapetsas, Ioannis N.

doi:10.1002/mrc.4426

Cited by 6 publications

(5 citation statements)

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“…Recently, Tsipis and Karapetsas proposed a non‐relativistic protocol to predict the Pt‐195 chemical shift. The GIAO‐PBE0/SARC‐ZORA(Pt)/6‐31 + G(d)(Ligands)/PCM level was used in the calculations using the GAUSSIAN 09 program.…”

Section: Resultssupporting

confidence: 55%

“…Only C‐13 and N‐15 chemical shifts were calculated and the role of solvent and relativistic effects on the NMR parameters for light nuclei was stressed. Recently, Tsipis and Karapetsas reported a non‐relativistic DFT computational protocol to predict Pt‐195 NMR chemical shift. For a series of Pt(II) and Pt(IV) complexes, Pt‐195 chemical shifts were computed employing the GIAO‐PBE0/SARC‐ZORA(Pt)U6‐31 + G(d)(Ligands)/PCM non‐relativistic level.…”

Section: Introductionmentioning

confidence: 99%

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Predicting Pt‐195 NMR chemical shift using new relativistic all‐electron basis set

et al. 2016

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Predicting NMR properties is a valuable tool to assist the experimentalists in the characterization of molecular structure. For heavy metals, such as Pt-195, only a few computational protocols are available. In the present contribution, all-electron Gaussian basis sets, suitable to calculate the Pt-195 NMR chemical shift, are presented for Pt and all elements commonly found as Pt-ligands. The new basis sets identified as NMR-DKH were partially contracted as a triple-zeta doubly polarized scheme with all coefficients obtained from a Douglas-Kroll-Hess (DKH) second-order scalar relativistic calculation. The Pt-195 chemical shift was predicted through empirical models fitted to reproduce experimental data for a set of 183 Pt(II) complexes which NMR sign ranges from -1000 to -6000 ppm. Furthermore, the models were validated using a new set of 75 Pt(II) complexes, not included in the descriptive set. The models were constructed using non-relativistic Hamiltonian at density functional theory (DFT-PBEPBE) level with NMR-DKH basis set for all atoms. For the best model, the mean absolute deviation (MAD) and the mean relative deviation (MRD) were 150 ppm and 6%, respectively, for the validation set (75 Pt-complexes) and 168 ppm (MAD) and 5% (MRD) for all 258 Pt(II) complexes. These results were comparable with relativistic DFT calculation, 200 ppm (MAD) and 6% (MRD). © 2016 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 55%

Section: Introductionmentioning

confidence: 99%

Predicting Pt‐195 NMR chemical shift using new relativistic all‐electron basis set

et al. 2016

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“…Previously, an exhaustive assessment of the performance of diverse computational protocols based on density functional theory (DFT) for the computation of 195 Pt chemical shifts for a series of Pt II and Pt IV complexes revealed the good performance of the GIAO‐PBE0/SARC‐ZORA(Pt)∪6‐31+G(d)(E)/PCM computational protocol. On this basis, we applied DFT computational protocols for the calculation of 15 N NMR chemical shifts of nitrato and aquanitrato complexes of PGMs existing in NASs.…”

Section: Introductionmentioning

confidence: 99%

Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative¹⁵N NMR and DFT Study

2018

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The accurate prediction of 15N nuclear magnetic resonance (NMR) chemical shifts for three sets of nitrato and mixed‐ligand aquanitrato rhodium (9 complexes), palladium (11 complexes) and platinum (11 complexes) systems was achieved using density functional theory (DFT) calculations employing the GIAO‐PBE0/ADZP(M)∪6‐31+G(d)(E)/PCM (M = Rh, Pd, or Pt, E = main group element) computational protocol. A comparison of δcalcd 15N NMR chemical shifts with δexptl 15N NMR chemical shifts reveals that the DFT calculations correctly predict the division of signals into two groups, the first one involving the PdII, PtII, and RhIII nitrato complexes, and the second the PtIV and PdIV nitrato complexes. Hydrogen bonds and the number of nitrato ligands and their coordination mode remarkably affect the δcalcd 15N chemical shift. Generally, the experimentally observed chemical shifts are found in a sufficiently narrower range for each metal center in comparison to the calculated ones due to an averaging action of the outer‐sphere interactions of complexes with external molecules of water and nitric acid.

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“…Other calculations performed Zhao et al for diazido-platinum(IV) complexes where vibrational modes determined by the TD-DFT(PBE1PBE/LanL2DZ/C-PCM) model confirmed the dissociative character of the low-lying excited states connected with metal–ligand charge transfer (LMCT) of azido-ligands. Series of papers was recently published by Tsipis et al. , where 195 Pt NMR chemical shifts were determined for a large set of platinum complexes (both Pt(II) and Pt(IV)) in implicit water solution and compared with measured data. Similar calculations were also performed by Vicha et al using the PBE0/TZP/COSMO computational level with the two-component zeroth-order regular approximation.…”

Section: Introductionmentioning

confidence: 99%

Side Reactions with an Equilibrium Constraint: Detailed Mechanism of the Substitution Reaction of Tetraplatin with dGMP as a Starting Step of the Platinum(IV) Reduction Process

Šebesta

Burda

2017

J. Phys. Chem. B

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Two possible pathways of the substitution reaction within the reduction process of the Pt(DACH)Cl by dGMP are compared: associative reaction course and autocatalytic Basolo-Pearson mechanisms. Since two forms: single-protonated and fully deprotonated phosphate group of dGMP are present in equilibrium at neutral and mildly acidic solutions, consideration of a side reactions scheme with acido-basic equilibrium-constraint is a very important model for obtaining reliable results. The examined complexes are optimized at the B3LYP-GD3BJ/6-31G(d) level with the COSMO implicit solvation model and Klamt's radii used for cavity construction. Energy characteristics and thermodynamics for all reaction branches are determined using the B3LYP-GD3BJ/6-311++G(2df,2pd)/IEF-PCM/scaled-UAKS level with Wertz's entropy corrections. Rate constants are estimated for each individual branch according to Eyring's transition state theory (TST), averaged according to equilibrium constraint and compared with available experimental data. The determined reaction barriers of the autocatalytic pathway fairly correspond with experimental values. Furthermore, autocatalytic reaction of tetraplatin and its two analogues complexes [Pt(en)Cl and Pt(NH)Cl] are explored and compared with measured data in order to examined general reaction descriptors.

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Prediction of¹⁹⁵Pt NMR chemical shifts of dissolution products of H₂[Pt(OH)₆] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Cited by 6 publications

References 40 publications

Predicting Pt‐195 NMR chemical shift using new relativistic all‐electron basis set

Predicting Pt‐195 NMR chemical shift using new relativistic all‐electron basis set

Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative¹⁵N NMR and DFT Study

Side Reactions with an Equilibrium Constraint: Detailed Mechanism of the Substitution Reaction of Tetraplatin with dGMP as a Starting Step of the Platinum(IV) Reduction Process

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Prediction of195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Cited by 6 publications

References 40 publications

Predicting Pt‐195 NMR chemical shift using new relativistic all‐electron basis set

Predicting Pt‐195 NMR chemical shift using new relativistic all‐electron basis set

Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative15N NMR and DFT Study

Side Reactions with an Equilibrium Constraint: Detailed Mechanism of the Substitution Reaction of Tetraplatin with dGMP as a Starting Step of the Platinum(IV) Reduction Process

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Prediction of¹⁹⁵Pt NMR chemical shifts of dissolution products of H₂[Pt(OH)₆] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative¹⁵N NMR and DFT Study