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

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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.

10.1163/15685670260373335
/content/journals/10.1163/15685670260373335
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/content/journals/10.1163/15685670260373335
2002-08-01
2017-06-25

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