Impact of ligand protonation on higher-order metal complexation kinetics in aqueous systems

R.M. Town, H.P. van Leeuwen

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The impact of ligand protonation on the complexation kinetics of higher-order complexes is quantitatively described. The theory is formulated on the basis of the usual situation for metal complex formation in aqueous systems in which the exchange of water for the ligand in the inner coordination sphere is rate-determining (Eigen mechanism). We derive expressions for the general case of lability of MLn species that account for the contributions from all outer-sphere complexes to the rate of complex formation. For dynamic complexes, dissociation of ML is usually the rate-determining step in the overall process MLn ¿ M. Under such conditions, it is the role of ligand protonation in the step ML ¿ M that is relevant for the kinetic flux. 1:2 complexes of Cd(II) with pyridine-2,6-dicarboxylic acid fall into this category, and their lability at a microelectrode is reasonably well predicted by the differentiated approach. For non-dynamic systems, the kinetic flux arising from dissociation of higher-order complexes contributes to the rate-determining step. In this case, the weighted contribution of protonated and unprotonated outer-sphere complexes in all contributing dissociation reactions must be taken into account. The kinetic flux arising from the dissociation of 1:2 complexes of Ni(II) with bicine at a conventional electrode was quite well described by this combined approach. The results establish the generic role of ligand protonation within the overall framework of metal complexation kinetics in which complexes may be dynamic to an extent that depends on the operational time scale of the measurement technique.
Original languageEnglish
Pages (from-to)2563-2571
JournalThe Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment, & General Theory
Issue number12
Publication statusPublished - 2008


  • deposition potential sscp
  • state planar diffusion
  • stripping chronopotentiometry
  • dipicolinic acid
  • reversible electrodeposition
  • voltammetric lability
  • 5-nitrosalicylic acid
  • speciation analysis
  • buffers
  • nickel


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