Reaction-Kinetics of Macrocyclic Silver(ii) ...
|Title||Reaction-Kinetics of Macrocyclic Silver(ii) Complexes .1. Acid Aquation of the [Ag(ii)(anen4)]2+ Cation and its Reaction with Peroxodisulfate|
|Author(s)||R. Haines, M. Park|
|Journal||Journal of Coordination Chemistry|
|Abstract||The decomposition kinetics of the [Ag(II)L]2+ cation (where L = aneN4) has been studied as a function of [H+] and temperature, in aqueous perchlorate media (ionic strength = 1.00 mol dm-3). The decomposition follows the second-order rate, law, Rate = k[H+][Ag(II)L2+], where k = (6.65 +/- 0.11) x 10(-6) dm3 mol-1 s-1 at 298.2 K. From the temperature dependence, an activation energy of 89.0 +/- 0.7 kJ mol-1 has been determined. The silver(II) complex reaction with peroxodisulphate has also been studied in aqueous perchlorate media. This second-order reaction has an activation energy of 45.6 +/- 3.4 kJ mol-1. The mechanism may be described by reactant ion-pairing followed by a rate-determining step involving silver(II) complex-assisted peroxo-bond fissure.|
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