D. Bublitz et al., PREPARATION, PT-195 NMR, IR, RAMAN-SPECTR A, AND NORMAL-COORDINATE ANALYSIS OF THE COMPLEX-IONS [PTHND6-N](2-), N=0-6, Zeitschrift fur anorganische und allgemeine Chemie, 623(2), 1997, pp. 184-190
Citations number
10
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Zeitschrift fur anorganische und allgemeine Chemie
The extremely air and moisture sensitive hexahydridodeuteridoplatinate
s(IV) K-2[PtHnD6-n], n = 0-6, have been prepared by high pressure reac
tions 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 vary
ing 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 mix
ed ligand spheres are arranged systematically with an average high fie
ld shift of -9.5 ppm per substituted hydride ligand. By quantitative e
valuation of the integrated intensities the statistical formation of t
he individual complexions within the mixtures is derived. The molecula
r vibrations in the IR and Raman spectra of the pure homoleptic compou
nds 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.