Issue 6, 1974

Redox decomposition of trans-tetra-ammineaquosulphitocobalt(III) in aqueous solution

Abstract

The complex trans-[Co(NH3)4(H2O)(SO3)]+ decomposes to Co2+ in aqueous acid solution. Kinetic plots exhibit an initial period of curvature followed by a first-order process, kobs=(1·14 ± 0·03)× 10–4 s–1 at 25·0 °C, ΔH‡= 26·5 ± 0·1 kcal mol–1, and ΔS‡= 12·5 ± 0·4 cal K–1 mol–1[I= 1·00M(LiClO4)]. The rate of reaction is independent of [H+] in the range 0·01–1·00M. A mechanism is proposed relating kobs to a rate-determining isomerisation to the cis-complex, followed by rapid conversion to the complex [Co(NH3)3(H2O)2(SO3)]+ which probably undergoes an internal redox reaction. Somewhat higher rates have been observed in the presence of molecular oxygen and evidence is presented for formation of the free radical HSO3.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1974, 647-651

Redox decomposition of trans-tetra-ammineaquosulphitocobalt(III) in aqueous solution

M. A. Thacker, K. L. Scott, M. E. Simpson, R. S. Murray and W. C. E. Higginson, J. Chem. Soc., Dalton Trans., 1974, 647 DOI: 10.1039/DT9740000647

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