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By reaction of [PtBr 4 ] 2-  with XeF 2  in dichloromethane product mixtures containing nine fluoro-chloro-, four fluoro-bromo- and 15 fluoro-chloro-bromo-platinates(IV) are formed. All complexes are detectable by in situ  l9 F NMR measurements. Due to the increasing trans influence F &lt; Cl &lt; Br, the signals &lt;5( 19 F) of symmetric F-Pt-F axes observed at highest field are shifted downfield on the average by 93 ppm as compared with δ( 19 F • ) of F •• Pt-Cl′ axes, and further to lower field by 40 ppm for &lt;5(F •• ) of F •• -Pt-Br″ axes. For the same reason the coupling constant  1 J(F •• Pt) ≈ 1099 Hz is by 13.3 % smaller than  1 J(F • Pt) ≈ 1268 Hz, which is by 32.3 % smaller than δ(FPt) ≈ 1873 Hz. Based on the axis method, and taking into account characteristic increments of chemical shifts depending on cis influences, the calculation of the  195 Pt NMR signals of 27 observed species of the system [PtF n Cl 6-n-m Br m ] 2-  n, m = 0 - 6, has been successful. The  195 Pt NMR shifts of further 29 so far not detected complexes are predicted. Using parameters depending on the geometry of the complex, the  19 F NMR shifts of 28 F-containing platinates(IV) have been calculated in good agreement with the experimental data.  19 F resonances are predicted for 19 so far missing complexes.

zeitschrift für naturforschung b

Berechnung der  19 F- und  195  Pt-NMR-Verschiebungen von FIuoro-Chloro-Bromo-Platinaten(IV) / Calculation of  19 F and  195 Pt NMR Shifts of Fluoro-Chloro-Brom o-Platinates(IV )