Abstract
The kinetics of the acid-catalysed dissociation of CuII complexes of four N,N′-dialkyl-1,10-phenanthroline-2,9-dimethanamine ligands (alkyl = Me, Et, i-Pr, t-Bu) have been studied using a stopped-flow spectrophotometer in 6.6 × 10−3 ∼ 0.5 mol dm−3 HCl (I = 0.5 mol dm−3 HCl + NaCl) over a range of temperatures. The kinetic data can be fitted to the rate expression kobs = kK′2[H+]/(1 + K′2[H+]). The acid dissociation can be rationalized in terms of a six-step kinetic process involving rapid pre-equilibrium cleavage of the two CuII–N(aliphatic amine) bonds, two rapid pre-equilibrium protonations and rate-determining cleavage of the CuII–N(phenanthroline) bond. The temperature dependence of the rate was determined and the appropriate thermodynamic parameters obtained.
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