Formation and characterization of platinum(III)-ethylenediamine complex ions using pulse radiolysis

Journal Article · Fri Oct 31 23:00:00 EST 1980 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50213a017· OSTI ID:6468328

Waltz, W L ^[1]; Lilie, J; Walters, R T; Woods, R J

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1. Univ. of Saskatchewan, Saskatoon

Pulse radiolysis experiments using conductivity, polarographic and uv-visible absorption detection techniques have been carried out on the reaction of hydroxyl radical with bis(ethylenediamine)platinum(II)perchlorate in aqueous media. This reaction is shown to proceed by OH addition to the platinum center to yield a nascent product where the metal is in a formal oxidation state of III. The subsequent behavior of this Pt(III) transient generates three additional transients, whose formations are dependent upon the pH and presence of free chloride ion. A mechanism is proposed whereby these transients are interrelated through acid-base, chloride substitution, and water elimination processes. Evidence is presented to support the classification of the Pt(III) species into two groups having the compositions of Pt(en)/sub 2/(X)/sup n+/ (X = OH, H/sub 2/O, Cl; n = 2,3) and Pt(en)(en-H)/sup 2 +/ (en-H = /sup -/NHCH/sub 2/CH/sub 2/NH/sub 2/). For the former group, the respective wavelength maxima and molar absorption coefficients are 270 nm, ca. 4500 M/sup -1/ cm/sup -1/ (X = OH), < 250 nm (X = H/sub 2/O), and 260 nm, 8000 M/sup -1/ cm/sup -1/ (X = Cl). For Pt(en)(en-H)/sup 2 +/, two absorption bands are found with peaks at 340 nm (2900 M/sup -1/ cm/sup -1/) and 480 nm (1500 M/sup -1/ cm/sup -1/). This latter species is also the major product of the reaction of the hydrated electron and trans-di-hydroxobis(ethylenediamine) platinum(IV) perchlorate which was investigated by absorption and conductivity techniques. The possible structures of these intermediates are discussed.

• OSTI ID: 6468328
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 19:11; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ABSORPTION SPECTROSCOPY
AMINES
AQUEOUS SOLUTIONS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPOUNDS
COMPLEXES
DATA
DECOMPOSITION
DISPERSIONS
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
EXPERIMENTAL DATA
GRAPHS
HALOGEN COMPOUNDS
HYDROXYL RADICALS
INFORMATION
MIXTURES
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORATES
PHYSICAL PROPERTIES
PLATINUM COMPLEXES
PLATINUM COMPOUNDS
POLAROGRAPHY
PULSE TECHNIQUES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
SOLUTIONS
SPECTROSCOPY
TABLES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS