Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

X. cap alpha. method as a tool for structure elucidation of short-lived transients generated by pulse radiolysis or flash photolysis. 2. Oxidative reactions of PtCl/sub 4//sup 2 -/

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00201a017· OSTI ID:5622391
; ; ;
Relativistic MS-X..cap alpha.. calculations have been performed on Pt(III) complexes used as models of the transients generated by pulse radiolysis of PtCl/sub 4//sup 2 -/ in water or in NaCl neutral and acidic solutions. These structures include the following complexes: (1) PtCl/sub 4/O/sup 3 -/, PtCl/sub 4/(OH)/sup 2 -/, PtCl/sub 5/(OH)/sup 3 -/; (2) PtCl/sub 4/(OH)/sub 2//sup 3 -/ or PtCl/sub 4/(OH)(H/sub 2/O)/sup 2 -/; (3) PtCl/sub 5//sup 2 -/, PtCl/sub 6//sup 3 -/. The calculated electronic structures and charge-transfer absorption spectra of these d/sup 7/ complexes are analyzed, especially in connection with the Pt/sup III/-O or Pt/sup III/-Cl/sub ax/ bond lengths. The comparison of the theoretical CT spectra with those obtained experimentally suggests that (1) the short-lived transient, generated by pulse radiolysis of neutral aqueous solutions of Pt/sup II/Cl/sub 4//sup 2 -/ and absorbing at 450 nm, is best described as PtCl/sub 4/(OH)(H/sub 2/O)/sup 2 -/ or PtCl/sub 4/(OH)/sub 2//sup 3 -/ and (2) the transient species observed in neutral or acidic solutions containing an excess of Cl/sup -/ anions and absorbing near 290 nm is consistent with the formulation of PtCl/sub 6//sup 3 -/ with moderate elongation of the Pt/sup III/-Cl/sub ax/ bond lengths (0.2 to 0.3 A). In both cases, only the hexacoordinated models can yield agreement with experimental spectra.
Research Organization:
Centre National de la Recherche Scientifique, ENSCM, Mulhouse, France; Lyon-1 Univ., Villeurbanne, France; Aix-Marseille St. Jerome Univ., France; Saskatchewan Univ., Saskatoon
OSTI ID:
5622391
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:7; ISSN INOCA
Country of Publication:
United States
Language:
English

Similar Records

Platinum(III) in the REOA mechanism of PtCl sub 4 sup 2 minus and PtCl sub 6 sup 2 minus. A pulse-radiolysis study
Journal Article · Wed Jul 26 00:00:00 EDT 1989 · Inorganic Chemistry; (USA) · OSTI ID:7107853
Photolytic and radiolytic study of platinum(III) complex ions containing aquo and chloro ligands
Journal Article · Wed Jun 14 00:00:00 EDT 1989 · Inorganic Chemistry; (USA) · OSTI ID:5143001
Kinetics and mechanism for photosubstitution of the (PtCl/sub 6/)/sup 2 -/ ion in acetonitrile
Journal Article · Thu Dec 31 23:00:00 EST 1987 · Kinet. Catal. (Engl. Transl.); (United States) · OSTI ID:6690788

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400500* -- Photochemistry
400600 -- Radiation Chemistry
ABSORPTION SPECTRA
CHARGE DISTRIBUTION
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DATA
DECOMPOSITION
ENERGY LEVELS
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
NUMERICAL DATA
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PLATINUM CHLORIDES
PLATINUM COMPLEXES
PLATINUM COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
REACTION INTERMEDIATES
SPECTRA
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS