The Mechanism and Kinetics of the Substitution of Azide, Thiocyanate, and Cyanide Ions in Aquopentacyanocobaltate(III) and Pentacyanohydroxocobaltate(III)

DOI: 10.1039/DT9810001578

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1578 - 1582 (1981)

Update date:2022-08-04

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Authors:

Burnett, Michael G.

Gilfillan, W. Matthew

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Article abstract of DOI:10.1039/DT9810001578

The substitution of pentacyanohydroxocobaltate(III), ^3-, by azide ion is shown to take place by the reaction of aquopentacyanocobaltate(III), ^2-, in equilibrium with it.Deviations from simple second-order rate laws for the substitution of azide, thiocyanate, and cyanide into ^2- at unit ionic strength and 40 deg 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.

Full text of DOI:10.1039/DT9810001578

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