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Title: 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]

Abstract

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.

Authors:
;
Publication Date:
Research Org.:
Univ. of Notre Dame, IN
OSTI Identifier:
5261128
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorg. Chem.; (United States); Journal Volume: 21:5
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 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)

Citation Formats

Morliere, P., and Patterson, L.K. 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]. United States: N. p., 1982. Web. doi:10.1021/ic00135a027.
Morliere, P., & Patterson, L.K. 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]. United States. doi:10.1021/ic00135a027.
Morliere, P., and Patterson, L.K. Sat . "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]". United States. doi:10.1021/ic00135a027.
@article{osti_5261128,
title = {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]},
author = {Morliere, P. and Patterson, L.K.},
abstractNote = {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.},
doi = {10.1021/ic00135a027},
journal = {Inorg. Chem.; (United States)},
number = ,
volume = 21:5,
place = {United States},
year = {Sat May 01 00:00:00 EDT 1982},
month = {Sat May 01 00:00:00 EDT 1982}
}