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The oxidation reaction in X-irradiated bis(ethylenediamine)platinum(II) bis(hydrogen squarate): A single-crystal EPR study of a platinum(III) complex

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00050a025· OSTI ID:6826669
; ; ;  [1]; ;  [2];  [3];  [4]
  1. Universite de Geneve (Switzerland)
  2. Universite Paul Sabatier, Toulouse (France)
  3. Universite de Geneve (Switzerland) Universite Claude Bernard, Villeurbanne (France)
  4. Universite Claude Bernard, Villeurbanne (France)
+ Show Author Affiliations

A large single crystal of bis(ethylenediamine)platinum bis(hydrogen squarate) ([Pt(en)[sub 2]](HSq)[sub 2]), has been X-irradiated at 77 K and studied by EPR. The g and [sup 195]Pt hyperfine tensors obtained from the angular dependence of the spectrum are consistent with the trapping of a Pt(III) complex containing the unpaired electron in a d[sub z[sup 2]] orbital. Comparison of the orientations of the eigenvectors with those of the crystallographic interatomic vectors together with the predictions of X[alpha] calculations on the model complex [Pt(NH[sub 3])[sub 4](OH)[sub 2]][sup +] leads to a mechanism whereby a radiogenic radical, formed by homolytic scission of the hydrogen squarate hydroxyl, oxidizes the Pt(en)[sub 2] dication and yields [Pt(en)[sub 2](Sq)](HSq).

OSTI ID:
6826669
Journal Information:
Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:24; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400600* -- Radiation Chemistry
CATIONS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
COMPLEXES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
INFORMATION
IONIZING RADIATIONS
IONS
MAGNETIC RESONANCE
MATHEMATICAL MODELS
NUMERICAL DATA
OXIDATION
PLATINUM COMPLEXES
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
RESONANCE
THEORETICAL DATA
TRANSITION ELEMENT COMPLEXES
X RADIATION