Superoxide reactions with (isonicotinamide) pentaammineruthenium (II) and -(III)
The reactions of superoxide with (Ru(NH/sub 3/)/sub 5/isn)/sup 2 +/ and (Ru(NH/sub 3/)/sub 5/isn)/sup 3 +/ have been investigated in aqueous solution (..mu.. = 0.1 M (formate buffer) at 23 +- 2/sup 0/C with use of pulse radiolysis). The radical HO/sub 2/ oxidizes Ru(II) with a rate constant of 9.07 x 10/sup 6/ M/sup -1/s/sup -1/, and O/sub 2//sup -/ reduces Ru(III) with a rate constant of 2.18 x 10/sup 8/M/sup -1/s/sup -1/. These values are in good agreement with those deduced from a study of the reaction of O/sub 2/ with (Ru(NH/sub 3/)/sub 5/isn)/sup 2 +/, and this agreement confirms many of the conclusions about the reaction mechanism arrived at from the latter study. Outer-sphere reductions of HO/sub 2/ to HO/sub 2//sup -/ are shown to be anomalous from the perspective of the Marcus theory. Approximate values have also been obtained for the specific rates governing the reactions of Ru(III) with OH, H, e/sub aq//sup -/, CO/sub 2//sup -/, and HC(OH)/sub 2/ and of Ru(II) with OH.
- OSTI ID:
- 6468343
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 19:12; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400600* -- Radiation Chemistry
ALKALI METAL COMPOUNDS
AMIDES
AMINES
AQUEOUS SOLUTIONS
AZINES
BUFFERS
CARBOXYLIC ACID SALTS
CARBOXYLIC ACIDS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DECOMPOSITION
DISPERSIONS
FORMATES
FORMIC ACID
HETEROCYCLIC COMPOUNDS
KINETICS
MEDIUM TEMPERATURE
MIXTURES
MONOCARBOXYLIC ACIDS
NICOTINAMIDE
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
RUTHENIUM COMPLEXES
SODIUM COMPOUNDS
SOLUTIONS
SUPEROXIDE RADICALS
TRANSITION ELEMENT COMPLEXES
VITAMIN B GROUP
VITAMINS