Effect of nitrilotriacetate on the mechanism of reduction of copper(II) ions by. cap alpha. -hydroxyalkyl free radicals via complexes with copper-carbon bonds as intermediates. Pulse-radiolytic study. [Pulsed electrons]
..cap alpha..-Hydroxyalkyl free radicals, CR/sub 1/R/sub 2/OH, react with copper(II) nitrilotriacetate, Cu(nta)..sqrt..(aq), in aqueous solutions to form the unstable intermediates (nta)Cu/sup III/-CR/sub 1/R/sub 2/OH/sup -/(aq), or (nta)Cu/sup III/-CH/sub 2/O/sup 2 -/(aq). These intermediates decompose by reducing a second Cu/sup II/(nta)/sup -/(aq) complex, i.e. via the reaction (nta)Cu/sup III/-CR/sub 1/R/sub 2/OH/sup -/(aq) + Cu/sup I/(nta)..sqrt..(aq)H/sub 2/O/..-->.. Cu/sup I/(nta)/sup 2 -/(aq) + Cu/sup II/(nta)/sup -/(aq) + CR/sub 1/R/sub 2/O + H/sub 3/O/sup +/. Unexpectedly, the intermediates do not decompose via first-order processes as expected. The spectrum of (nta)Cu/sup III/-CH/sub 2/OH/sup -/(aq) is reported. The kinetics of reduction of Co(NH/sub 3/)/sub 6//sup 3 +/, Ru(NH/sub 3/)/sub 6//sup 3 +/, and Fe(CN)/sub 6//sup 3 -/ by the latter intermediate are reported. 23 references, 1 figure, 2 tables.
- Research Organization:
- Ben Gurion Univ. of the Negev, Beer-Sheva, Israel
- OSTI ID:
- 6731832
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:27; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400600* -- Radiation Chemistry
ALKYL RADICALS
CATIONS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
COPPER COMPOUNDS
DATA
DECOMPOSITION
ELECTRONS
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
HYDROXY COMPOUNDS
INFORMATION
IONS
IRRADIATION
LEPTONS
NUMERICAL DATA
ORGANIC COMPOUNDS
PULSED IRRADIATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REDUCTION
TRANSITION ELEMENT COMPOUNDS