Hydroxyl radical reactions with the nickel(II) macrocyclic complexes Ni/sup II/Cr, Ni/sup II/(CR-2H), and Ni/sup II/(CR + 4H). Generation of ligand radicals and nickel(III) species. [Gamma radiation]
Reactions of hydroxyl radicals with the three closely related nickel(II) macrocyclic complexes Ni/sup II/(CR-2H), Ni/sup II/(CR)(H/sub 2/O)/sub 2/, and Ni/sup II/(CR+4H) have been studied by pulse radiolysis. With use of spectral data from the Ni(III) forms of these complexes and the behavior of radiolytically generated intermediates toward O/sub 2/, it has been found that both Ni(III) species and ligand radicals may be produced. The reaction of Ni/sup II/CR(H/sub 2/O)/sub 2/ with OH gives evidence for formation of ligand radical alone. By contrast. OH attack on Ni/sup II/(CR-2H) and Ni/sup II/(CR+4H) produces Ni(III) intermediates as well as ligand radicals through competitive pathways. The generation of a Ni(III) intermediate appears to parallel the absence of solvent binding at axial positions in the parent Ni(II) complexes. Such behavior may be linked to steric effects and/or electronic considerations.
- Research Organization:
- Univ. of Notre Dame, IN
- OSTI ID:
- 5261128
- Journal Information:
- Inorg. Chem.; (United States), Vol. 21:5
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HYDROXYL RADICALS
CHEMICAL REACTIONS
NICKEL COMPLEXES
WATER
RADIOLYSIS
BUFFERS
HETEROCYCLIC COMPOUNDS
LIGANDS
PH VALUE
PULSED IRRADIATION
REACTION INTERMEDIATES
CHEMICAL RADIATION EFFECTS
CHEMISTRY
COMPLEXES
DECOMPOSITION
HYDROGEN COMPOUNDS
IRRADIATION
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
TRANSITION ELEMENT COMPLEXES
400600* - Radiation Chemistry
400201 - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)