Theoretical studies on vibrational spectra of mixed cyanide–halide complexes of platinum(IV) and palladium(IV)

Abstract

The vibrational spectra of mixed cyanide–halide complexes, M(CN) 4X 2 2− and M(CN) 5X 2− (M=Pt and Pd; X=F, Cl, Br and I), have been systematically investigated by ab initio RHF, B3LYP and MP2 methods with LanL2DZ and SDD basis sets. The calculated vibrational frequencies of platinum complexes are evaluated via comparison with the experimental values. In the infrared frequency region, the CN stretching vibrational frequencies calculated at B3LYP level with two basis sets are in good agreement with the observed values with deviations, −16–4 cm −1 for Pt(CN) 4X 2 2− and −18 to −2 cm −1 for Pt(CN) 5X 2−. However, in far-infrared region, the results obtained at RHF level are better than those calculated at B3LYP and MP2 levels. For RHF/SDD method, the deviations for PtX and PtC stretching vibrational frequencies are −14–1 and −12 to −2 cm −1 in the complex Pt(CN) 4X 2 2−, −19 to −11 and −15–14 cm −1 in the Pt(CN) 5X 2− complex, respectively. The vibrational frequencies of palladium(IV) and some platinum(IV) complexes that have not been experimentally reported are predicted.