Elsevier

Polyhedron

Volume 7, Issue 13, 1988, Pages 1197-1202
Polyhedron

The pentacyanonitrosylferrate ion—V. The course of the reactions of nitroprusside with a range of thiols

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Abstract

Thiols RSH (RSH = MeSH, cysteine, N-acetylcysteine, 2-methylcysteine, N-acetyl-2-methylcysteine, penicillamine, N-acetylpenicillamine and glutathione) react with nitroprusside ([Fe(CN)5NO]2−, pentacyanonitrosylferrate (2−)) to give, via the intermediates [Fe(CN)5N(O)SR]3− and [Fe(CN)5NO]3−, the pentacoordinate iron(I) complex [Fe(CN)4NO]2−. The fate of this complex depends crucially upon the reaction conditions; in the presence of oxygen, [Fe(CN)4NO]2− can reform [Fe(CN)5NO]2− to give an effective stoichiometry of RS to [Fe(CN)5NO]2− substantially greater than 1 : 1 ; in the absence of oxygen and with a stoichiometric ratio of 1 : 1, the [Fe(CN)4NO]2− follows a well established pathway to yield [Fe(CN)6]4−, Fe2+ and NO; in the absence of oxygen and with an excess of the RS ligand, substitution occurs at [Fe(CN)4NO]2− to give firstly [Fe(NO)2(SR)2] and subsequently [Fe2(SMe)[in2(NO)4] (where R = Me) or [Fe4S3(NO)7] (when R = H). For every R except R = H, decomposition of the initial adduct [Fe(CN)5N(O)SR]3− yields the disulphide RSSR; when R = H, elemental sulphur is formed.

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