title: 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)5X2- (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)5X2-. 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 Ptz.sbnd;X and Ptz.sbnd;C stretching vibrational frequencies are -14-1 and -12 to -2 cm(-1) in the complex Pt(CN)4X2 2-, -19 to -11 and -15-14 cm(-1) in the Pt(CN)5X2- complex, respectively. The vibrational frequencies of palladium(IV) and some platinum(IV) complexes that have not been experimentally reported are predicted.
authors.affiliation: State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University, 210093, Jiangsu, Nanjing, People's Republic of China.
authors.forename: Yu
authors.initials: Y
authors.lastname: Zhang
authors.forename: Lin
authors.initials: L
authors.lastname: Zhang
authors.forename: Hanbing
authors.initials: H
authors.lastname: Tao
authors.forename: Xiaojuan
authors.initials: X
authors.lastname: Sun
authors.forename: Longgen
authors.initials: L
authors.lastname: Zhu
mesh_terms: D003486:Cyanides / Q000737:chemistry; D006219:Halogens / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D009944:Organoplatinum Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
chemical_list: D003486:Cyanides; D006219:Halogens; D009942:Organometallic Compounds; D009944:Organoplatinum Compounds; D010165:Palladium