Hydrogen abstraction and one-electron oxidation in nickel(II)-iminodiacetate complexes

Journal Article · Thu Feb 05 04:00:00 EST 1981 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j150603a017· OSTI ID:6611931

Bhattacharyya, S N; Saha, N C; Neta, P

Reactions of nickel(II) iminodiacetates with OH radicals in aqueous solutions were studied by means of steady-state and pulse radiolysis. Radiolytic degradation of the complexes led to the formation of glycine and carbonyl compounds with similar yields. The OH radical attacks the metal complexes at the ligand rather than at the metal center, the product being a metal-coordinated radical. This carbon-centered radical undergoes disproportionation into products. It may be also oxidized by O/sub 2/ and Fe(CN)/sub 6//sup 3 -/. In the presence of N/sub 2/O the radical initiates a chain reaction in the case of the 1:1 complex but not with the 1:2 complex or the free ligand. Unlike OH, Br/sub 2//sup -/ attacks the metal center rather than the ligand and oxidizes it to the Ni/sup III/ complexes. This reaction is followed by oxidation of the carboxyl group of the ligand by the Ni/sup III/ to result in decarboxylation and production of formaldehyde.

• Research Organization: Univ. of Notre Dame, IN
• OSTI ID: 6611931
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:3; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ALDEHYDES
AMINO ACIDS
CARBONYLS
CARBOXYLIC ACIDS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DECOMPOSITION
FORMALDEHYDE
GLYCINE
HYDROXYL RADICALS
IRRADIATION
NICKEL COMPLEXES
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXIDATION
PULSED IRRADIATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
TRANSITION ELEMENT COMPLEXES
YIELDS