Issue 0, 1968

The mechanism of the chloride- and bromide-catalysed disproportionation of the µ-amido-µ-peroxo-bis{bis(ethylenediamine)cobalt(III)} complex in aqueous solutions

Abstract

Details of experiments relating to the mechanism of the chloride- and bromide-catalysed disproportionation of the peroxo-dicobalt complex (en)2Co·µ(NH2,O2)·Co(en)23+ at temperatures in the range 10–25°, and in aqueous perchloric acid media, µ 3·0M(LiClO4), are considered. In the chloride-catalysed reaction, with [Cl]= 0·02–2·0M the overall change is: [graphic omitted] where the amido-hydroxo-bridged complex which is formed is in equilibrium with the aquo-chloro-complex: [graphic omitted] Yields of the superoxo-complex are generally between 60 and 66%, in accordance with (i). In the bromide-catalysed reaction, with [Br]= 0·1–1·0M, similar reactions are effective but yields of the superoxo-complex are generally much smaller and in some cases less than 15%. Hypochlorous and hypobromous acids are believed to be formed as intermediates in the reactions. Low yields which are observed with bromide ions can be explained by considering the equilibrium: H++ Br+ HOBr H2O + Br2(aq)(K 1·7 × 108 mole–2|2). The reaction of hypobromous acid with the peroxo-complex may be slower than that of hypochlorous acid.

Article information

Article type
Paper

J. Chem. Soc. A, 1968, 2840-2847

The mechanism of the chloride- and bromide-catalysed disproportionation of the µ-amido-µ-peroxo-bis{bis(ethylenediamine)cobalt(III)} complex in aqueous solutions

R. Davies and A. G. Sykes, J. Chem. Soc. A, 1968, 2840 DOI: 10.1039/J19680002840

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