Electron transfer, 151. Decomposition of peroxynitrite as catalyzed by copper(II)

Electron transfer, 151. Decomposition of peroxynitrite as catalyzed by copper(II) The decomposition of peroxynitrite in aqueous solution at pH 9.8–11.1 is catalyzed by copper(II) at the 10–7–10–6 M level. In the presence of added ammonia (0.03 M) or imidazole (0.005 M), reaction rates were as much as 160 times as great as those in copper-free systems. Catalysis was strongly inhibited by glycine, 2,2-bipyridyl, and EDTA. The yield of nitrite from the decomposition, [NO¯2]/[O=NOO¯]taken = 0.26, did not vary significantly with pH or [CuII]. Variation of reaction rates with [H+] and [CuII] is consistent with partition of the catalyst into an acidic form, (cat)HA (pKA 10.2–10.5), a dimer, (catHA)2, and a basic form (cat)A; only the first of these is active. Both transformations are taken to be initiated by CuII-induced homolysis of the O—O bond in peroxynitrite, yielding the reactive intermediate, a species of the type CuIII(OH). The latter may react further with peroxynitrite (ultimately yielding NO¯2 and O2) or with nitrite (yielding NO¯3). It is further suggested that catalytic activity of the type observed requires a substitution-labile CuII(OH2) function. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Electron transfer, 151. Decomposition of peroxynitrite as catalyzed by copper(II)

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Publisher
Brill Academic Publishers
Copyright
Copyright © 2002 by VSP 2002
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/15685670260373335
Publisher site
See Article on Publisher Site

Abstract

The decomposition of peroxynitrite in aqueous solution at pH 9.8–11.1 is catalyzed by copper(II) at the 10–7–10–6 M level. In the presence of added ammonia (0.03 M) or imidazole (0.005 M), reaction rates were as much as 160 times as great as those in copper-free systems. Catalysis was strongly inhibited by glycine, 2,2-bipyridyl, and EDTA. The yield of nitrite from the decomposition, [NO¯2]/[O=NOO¯]taken = 0.26, did not vary significantly with pH or [CuII]. Variation of reaction rates with [H+] and [CuII] is consistent with partition of the catalyst into an acidic form, (cat)HA (pKA 10.2–10.5), a dimer, (catHA)2, and a basic form (cat)A; only the first of these is active. Both transformations are taken to be initiated by CuII-induced homolysis of the O—O bond in peroxynitrite, yielding the reactive intermediate, a species of the type CuIII(OH). The latter may react further with peroxynitrite (ultimately yielding NO¯2 and O2) or with nitrite (yielding NO¯3). It is further suggested that catalytic activity of the type observed requires a substitution-labile CuII(OH2) function.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Oct 13, 2004

References

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