Oxidation of substituted alkyl radicals by IrCl/sub 6//sup 2 -/, Fe(CN)/sub 6//sup 3 -/, and MnO/sub 4//sup -/ in aqueous solution. Electron transfer versus chlorine transfer from IrCl/sub 6//sup 2 -/

Journal Article · Wed Mar 10 04:00:00 EST 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00369a017· OSTI ID:5582937

Steenken, S ^[1]; Neta, P

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1. Institut fuer Strahlenchemie in Max-Planck-Institut Fuer Kohlenforschung, Muelheim, Germany

Alkyl radicals substituted at C/sub ..cap alpha../ by alkyl, carboxyl, hydroxyl, alkoxyl, and chlorine react in aqueous solutions with Ir/sup IV/Cl/sub 6//sup 2 -/ to yield Ir(III) species. In the case of substitution by hydroxyl and alkoxyl, the rate constants are in the diffusion-controlled range ((4-6) x 10/sup 9/ M/sup -1/s/sup -1/) and the reaction proceeds by electron transfer. In the case of ethyl, methyl, carboxymethyl, and chloromethyl radicals the rate constants range from 3.1 x 10/sup 9/ for ethyl to 2.8 x 10/sup 7/M/sup -1/s/sup -1/ for trichloromethyl and the reaction proceeds by chlorine transfer from IrCl/sub 6//sup 2 -/ to the alkyl radical. With isopropyl and tert-butyll radicals the reaction proceeds by both electron and chlorine transfer. Alkyl radicals also react with Fe(CN)/sub 6//sup 3 -/. The rate constants increase strongly with increasing alkylation at C/sub ..cap alpha../ from 5 x 10/sup 6/ for methyl to 3.6 x 10/sup 9/M/sup -1/s/sup -1/ for tert-butyl, indicating that the transition state for the reaction is highly polar. Rate constants for reaction of MnO/sub 4//sup -/ with alkyl radicals are of the order 10/sup 9/M/sup -1/s/sup -1/. 4 figures, 1 table.

• OSTI ID: 5582937
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:5; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ALKYL RADICALS
ALKYLATION
AQUEOUS SOLUTIONS
CARBONIC ACID DERIVATIVES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE
CHLORINE COMPOUNDS
COMPLEXES
CYANATES
DECOMPOSITION
DISPERSIONS
ELECTRON EXCHANGE
ELECTRON TRANSFER
ELEMENTS
FERRICYANIDES
HALIDES
HALOGEN COMPOUNDS
HALOGENS
HYDROGEN COMPOUNDS
IRIDIUM CHLORIDES
IRIDIUM COMPOUNDS
IRON COMPLEXES
IRRADIATION
KINETICS
MANGANATES
MANGANESE COMPOUNDS
MIXTURES
NITROGEN COMPOUNDS
NONMETALS
ORGANIC COMPOUNDS
OXIDATION
OXYGEN COMPOUNDS
PULSED IRRADIATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
SOLUTIONS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
WATER