The one-electron reduction of pentacyanonitrosylferrate(II) ion, Fe(CN)5N02~(nitroprusside ion), in aqueous solution has been studied using continuous and pulse radiolysis techniques, the latter with optical absorption and kinetic conductivity detection. The reducing radicals eaq~, C02~, • 2 , (CH3)2ÓOH, and H react with Fe(CN)5N02™ (k = 1.0 X 10m, 4.0 X 10s, 6.7 X 108, 2.9 X 109, and 7 X 107 M™1 s™1, respectively) to yield Fe(CN)5N03~c haracterized by an absorption spectrum with Xmax 345 and 440 nm (emal 3.5 X 103 and 5.5 x 102 M4 cm™1, respectively); the spectrum is independent of pH (1-8.5). Fe(CN)5N03~undergoes first-order decay with the loss of CN™, presumably from the trans position, to form Fe(CN)4N02~(Xmax 615 nm, emax 3.8 X 102 M™1 cm™1) according to the following reactions: Fe(CN)5N03™ Fe(CN)4N02™ + CN™, K = 6.8 X 10~5; CN™ + H+ <=± HCN, K = 2.0 X 109. The observed first-order rate constant for the disappearance of Fe(CN)5N03™ (2.8 X 102 s™1) is independent of the nature of the reducing radical and pH (4.6-8.5); kobsd increases with increasing [H+] (> 10"4 M) or [CN™]. The relative concentrations of the two reduced species depend markedly on pH and [CN™], but not radiation dose. The reduced species are sensitive to 02 generating Fe(CN)5N02", Fe(CN)4NO(OH)2™, and polymeric species. In solutions c Fe(CN)5N03™ reacts rapidly with -CH2C(CH3)2OH (k = 2.Í cm™1), air-insensitive, moderately stable alkylnitroso complex, has been obtained in a KBr matrix.

One-Electron Reduction of Tris(2,2'-bipyridine) and Tris(1,10-phenanthroline) Complexes of Cobalt(III) in Aqueous Solution1

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Die Radiolyse sauerstofffreier wäßriger Lösungen der Komplexe (I) und (III) in Gegenwart organischer Verbindungen (RH) führt zu den Komplexen (II) und (IV).

Kinetik und Mechanismus der Reduktion von Cr(NH3)5NO(2+) durch Cr(2+) werden untersucht.

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