Reaction-kinetics of macrocyclic silver(ii) ...

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Title Reaction-kinetics of macrocyclic silver(ii) complexes .1. Acid aquation of the [Ag(ii)([15]anen4)]2+ cation and its reaction with peroxodisulfate
Author(s) Robert I. Haines, M. K. Park
Journal Journal of Coordination Chemistry
Date 1993
Volume 29
Issue 4
Start page 307
End page 317
Abstract The decomposition kinetics of the [Ag(II)L]2+ cation (where L = [15]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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