Abstract
The second-order rate constants for the direct replacement of halogens in halogenodiethylenetriamineplatinum(II) cations by dimethyl sulphide have been determined and the activation parameters calculated. The relative ease of replacement of the outgoing groups are found to follow the order Cl⪡Br⪡I, a pattern which depends entirely on activation entropy. The results are discussed in terms of an associative mechanism involving the formation of a five-coordinated intermediate, with second transition state rate-limiting. For the bromo complex, the kinetic studies are extended to di-butyl sulphides and the results provide further support for the associative mechanism.
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