The mechanism and kinetics of the substitution of azide, thiocyanate, and cyanide ions in aquopentacyanocobaltate(III) and pentacyanohydroxocobaltate(III)
- 1 January 1981
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 7,p. 1578-1582
- https://doi.org/10.1039/dt9810001578
Abstract
The substitution of pentacyanohydroxocobaltate(III), [Co(CN)5(OH)]3–, by azide ion is shown to take place by the reaction of aquopentacyanocobaltate(III), [Co(CN)5(OH2)]2–, in equilibrium with it. Deviations from simple second-order rate laws for the substitution of azide, thiocynate, and cyanide into [Co(CN)5(OH2)]2– at unit ionic strength and 40 °C are sufficiently small to be comparable with effects due to ionic activity variation and should not be accepted as evidence of a dissociative (D) mechanism. The reactions are reliably assigned to this class on the basis of activation volumes, solvent effects, and nucleophile competition experiments.Keywords
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