Reduction of alkaline aqueous disodium pentacyanonitrosylferrate(2–)(sodium nitroprusside) and kinetic features of its colour reaction with thiols
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 951-959
- https://doi.org/10.1039/dt9750000951
Abstract
The products of each one-electron step in the reduction of the anion [(NC)5FeIINO]2–, (I), to pentacyano-(hydroxylamine)ferrate(3–) ion, [(NC)5FeII(NH2OH)]3–, have been characterised spectroscopically. The anions [(NC)5Fe–ṄO]3– and [(NC)5Fe–N(H)Ȯ]4– have characteristic e.s.r. spectra; the anions [(NC)5Fe– O]4– and [(NC)5Fe(NH2OH)]3– have broadish optical absorption maxima at 347 and 436 nm respectively and hydrolyse slowly to the aquapentacyanoferrate(3–) anion, [(NC)5FeIIOH2]3–. The reduction processes resemble those of the stepwise reversible reduction of nitrobenzene to phenylhydroxylamine in alkali. Reversible reactions between (I) and thiolate anions give pink products, [(NC)5FeII(NO)SR]3–, which decompose irreversibly yielding [(NC)5Fe–ṄO]3– anions. The reactions (i) and (ii) may both be involved in these decompositions. [(NC)5Fe(NO)SR]3–→[(NC)5Fe–ṄO]3–+ RS·(i), [(NC)5Fe(NO)SR]3–+ RS–→[(NC)5Fe–NO]4–+ RS·SR (ii)Keywords
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