Preparation, Pt-195 NMR, IR, Raman spectra, and normal coordinate analysis of the complex ions [PtHnD6-n](2-), n=0-6

The extremely air and moisture sensitive hexahydridodeuteridoplatinates(IV) K-2[PtHnD6-n], n = 0-6, have been prepared by high pressure reactions at 500 degrees C and 1500 bar. The solid homoleptic compounds K-2[PtH6] and K-2[PtD6] and mixtures of K-2[PtHnD6-n] prepared with varying H/D ratios have been investigated by Pt-195(H-1) MAS NMR and by IR and Raman spectroscopy. Because of the high mobility of the atoms in the solid clearly resolved NMR spectra without sidebands are obtained exhibiting relatively sharp, isotropic Pt-195 resonances (Delta nu(1/2) = 400 Hz) at -990 +/- 1 ppm for K-2[PtH6] and -1034 +/- 1 ppm for K-2[PtD6]. Starting with K-2[PtH6] the signals of the complexes with mixed ligand spheres are arranged systematically with an average high field shift of -9.5 ppm per substituted hydride ligand. By quantitative evaluation of the integrated intensities the statistical formation of the individual complexions within the mixtures is derived. The molecular vibrations in the IR and Raman spectra of the pure homoleptic compounds and the heteroleptic species in the mixtures are assigned with the aid of normal coordinate analyses. The Pt-H valence force constant is 2.13 mdyne/Angstrom.