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Mechanistic Studies on the Oxidation of Nitrite by a μ-Oxodiiron(III,III) Complex in Aqueous Acidic Media

✍ Scribed by Jhimli Bhattacharyya; Subrata Mukhopadhyay

Publisher
John Wiley and Sons
Year
2005
Tongue
German
Weight
147 KB
Volume
88
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Examined in this study is the kinetics of a net 2e^−^ transfer between [Fe~2~(μ‐O)(phen)~4~(H~2~O)~2~]^4+^ (1) and its hydrolytic derivatives [Fe~2~(μ‐O)(phen)~4~(H~2~O)(OH)]^3+^ (2) and [Fe~2~(μ‐O)(phen)~4~(OH)~2~]^2+^ (3) with $\rm{{{NO}}_{{2}}^ - }$ in aqueous media and in presence of excess 1,10‐phenanthroline (phen). The reaction is quantitative with a 1 : 1 stoichiometry between the oxidant and reductant to produce ferroin ([Fe(phen)~3~]^2+^) and $\rm{{{NO}}_{{3}}^ - }$. The order of reactivity of the oxidant species is 1 > 2 > 3, in agreement with the progressive cationic charge reduction. The reactions appear to be inner‐sphere where the initial one‐electron proton‐coupled redox (1e^−^, 1H^+^; electroprotic) seems to be rate‐determining.

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