Ab Initio Calculations Of Hydroxoplatinum Compounds: I. Hexahydroxoplatinum(IV), (V), And (VI) Complexes. Pankratov D.A., Dement'ev A.I., Kiselev Yu.M. //Russian Journal of Inorganic Chemistry. 2008. V.53. №2. P.242-246.
The structural and spectral data on Pt(OH)6n clusters (n = -2, -1, 0) obtained by ab initio methods have been considered. The data for n = -2 are in good agreement with the published data for hexahydroxoplatinates (IV).
Previously, it was shown that oxidative synthesis in strongly basic mediums, and highly concentrated alkaline solutions of Pt(IV) leads to different dioxygen compounds containing the superoxo ligand (O2-). The structure of such compounds, existing primarily in solution, was confirmed by different physicochemical methods (for example, infrared and Raman spectroscopy, or EPR spectroscopy), which are not direct structural methods and are therefore only indirect evidence of the assumed structure.
To examine the structural and spectral features of binuclear platinum (IV) superoxo complexes, we performed full geometry optimization and calculated vibrational spectra by ab initio methods. In as much as the Pt(OH)6n ions are the structural units of the binuclear superoxo complexes in question, we also calculated Pt(OH)6n complexes, some of which have been structurally characterized.
Thus, using hexahydroxo complexes of platinum in different oxidation states as an example, we showed that the suggested computational method is valid for description of platinum-containing clusters and affords data consistent with the experimental data for known compounds.