A comparison of experimental and DFT calculations of ¹⁹⁵Pt NMR shielding trends for [PtX(n)Y(6-n)](2-) (X, Y = Cl, Br, F and I) anions
Copyright © 2010 John Wiley & Sons, Ltd.
| Veröffentlicht in: | Magnetic resonance in chemistry : MRC. - 1985. - 48 Suppl 1(2010) vom: 25. Dez., Seite S38-47 |
|---|---|
| 1. Verfasser: | |
| Weitere Verfasser: | , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2010
|
| Zugriff auf das übergeordnete Werk: | Magnetic resonance in chemistry : MRC |
| Schlagworte: | Comparative Study Journal Article Research Support, Non-U.S. Gov't Anions Halogens Platinum Compounds Platinum 49DFR088MY |
| Zusammenfassung: | Copyright © 2010 John Wiley & Sons, Ltd. A comparison between experimental and calculated gas-phase as well as the conductor-like screening model DFT (195)Pt chemical shifts of a series of octahedral [PtX(6-n)Y(n)](2-) complexes for X = Cl, Br, F, I was carried out to assess the accuracy of computed NMR shielding and to gain insight into the dominant σ(dia), σ(para) and σ(SO) shielding contributions. The discrepancies between the experimental and the DFT-calculated (195)Pt chemical shifts vary for these complexes as a function of the coordinated halide ions, the largest being obtained for the fluorido-chlorido and fluorido-bromido complexes, while negligible discrepancies are found for the [PtCl(6-n)Br(n)](2-) series; the discrepancies are somewhat larger where a significant deviation from the ideal octahedral symmetry such as for the geometric cis/trans or fac/mer isomers of [PtF(6-n)Cl(n)](2-) and [PtF(6-n)Br(n)](2-) may be expected. The discrepancies generally increase in the order [PtCl(6-n)Br(n)](2-) < [PtBr(6-n)I(n)](2-) < [PtCl(6-n)I(n)](2-) < [PtF(6-n)Br(n)](2-) ≈ [PtF(6-n)Cl(n)](2-), and show a striking correlation with the increase in electronegativity difference Δχ between the two halide ligands (X(-) and Y(-)) bound to Pt(IV) for these anions: 0.09 < 0.52 < 0.63 < 1.36 ≈ 1.27, respectively. The computed (195)Pt sensitivity to Pt-X bond displacement, ∂(δ(195)Pt)/∂(ΔPt-X), of these complexes is very large and depends on the halide ion, decreasing from 24 800, 18 300, 15 700 to 12 000 ppm/Å for [PtF(6)](2-), [PtCl(6)](2-), [PtBr(6)](2-) and [PtI(6)](2-), respectively |
|---|---|
| Beschreibung: | Date Completed 22.03.2011 Date Revised 21.11.2013 published: Print Citation Status MEDLINE |
| ISSN: | 1097-458X |
| DOI: | 10.1002/mrc.2607 |