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) | R. Haines, M. 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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