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Accurate prediction of 195Pt-NMR chemical shifts for hydrolysis products of [PtCl6]2− in acidic and alkaline aqueous solutions by non-relativistic DFT computational protocols

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The 195Pt-NMR chemical shifts of all possible hydrolysis products of [PtCl6]2− in acidic and alkaline aqueous solutions are calculated employing simple non-relativistic density functional theory computational protocols. Particularly, the GIAO-PBE0/SARC-ZORA(Pt) ∪ 6-31 + G(d)(E) computational protocol augmented with the universal continuum solvation model (SMD) performs the best for calculation of the 195Pt-NMR chemical shifts of the Pt(IV) complexes existing in acidic and alkaline aqueous solutions of [PtCl6]2−. Excellent linear plots of δ calcd(195Pt) chemical shifts versus δ exptl(195Pt) chemical shifts and δ calcd(195Pt) versus the natural atomic charge Q Pt are obtained. Very small changes in the Pt–Cl and Pt–O bond distances of the octahedral [PtCl6]2−, [Pt(OH)6]2−, and [Pt(OH2)6]4+ complexes have significant influence on the computed σ iso 195Pt magnetic shielding tensor elements of the anionic [PtCl6]2− and the computed δ 195Pt chemical shifts of [Pt(OH)6]2− and [Pt(OH2)6]4+. An increase of the Pt–Cl and Pt–O bond distances by 0.001 Å (1 mÅ) is accompanied by a downfield shift increment of 17.0, 19.4, and 37.6 ppm mÅ−1, respectively. Counter-anion effects in the case of the highly positive charged complexes drastically improve the accuracy of the calculated 195Pt chemical shifts providing values very close to the experimental ones.
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Keywords: 195Pt-NMR; DFT calculations; Hydrolysis products of [PtCl6]2− in aqueous solutions; Prediction of 195Pt chemical shifts

Document Type: Research Article

Affiliations: Laboratory of Inorganic and General Chemistry, Department of Chemistry, University of Ioannina, Ioannina, Greece

Publication date: November 2, 2015

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