Kinetics and mechanisms of the oxidation of Ni(II) and Cu(II) macrocycles by aquasilver(II) in acidic perchlorate media
Date of Original Version
The oxidation of NiIIcyclam, CuIIcyclam (cyclam = aneN4) and CuIICT (CT = Me6-4,11-dieneN4) by aquasilver(II) has been investigated kinetically in perchlorate media in the range [HClO4] = 1-4 mol dm-3. The reaction stoichiometry indicates 1 mol of oxidant reacting with 1 mol of M(II). Stopped-flow studies indicate a single reaction pathway involving MIIL + Ag2+ with k = 2.3 × 105, 3.5 × 105 and 1.5 × 104 dm3 mol-1 s-1 for NiIIcyclam, CuIIcyclan and CuIICT respectively, at 10 °C. While NiIIIcyclam is stable enough to allow UVVis characterization, CuIIIcyclam and CuIII decay by a first-order process with rate constants of 1.5 and 0.053 s-1 respectively. Reliable kinetic results could not be obtained for the oxidation of NiIICT by silver(II), but the oxidation product does, like NiIIIcyclam, have a significant lifetime. © 1987.
Publication Title, e.g., Journal
Inorganica Chimica Acta
Mentasti, Edoardo, and Louis J. Kirschenbaum. "Kinetics and mechanisms of the oxidation of Ni(II) and Cu(II) macrocycles by aquasilver(II) in acidic perchlorate media." Inorganica Chimica Acta 129, 1 (1987). doi: 10.1016/S0020-1693(00)85909-5.