Metal-ion recognition. Modeling the stability constants of some mixed-donor macrocyclic metal ion complexes—a simple model

La Trobe University Faculty of Science, Technology and Engineering Murray Darling Freshwater Research Centre

MDFRC item.

A procedure for modeling the stability constants of the Zn(II), Cd(II), Ag(I) and Pb(II) complexes of an extended series of 17-membered, mixed-donor macrocycles incorporating nitrogen, oxygen and/or sulfur donor atoms is presented. The ligands fall into two categories—those incorporating a symmetrical arrangement of their donor atom set (9 examples) and those in which the donor set has an unsymmetrical arrangement (5 examples). Metal stability constants for the former have been reported previously while corresponding data for the latter was determined as part of the present investigation. Initial computations were based on the 1:1 stability constants for the systems incorporating a symmetrical arrangement of their donor atom set. The approach employed was to assume that the overall free energy for metal complexation can be partitioned into the sum of contributions from individual metal–donor interactions. Thus for a given metal ion type, the log K data corresponding to each of these ligand systems were employed to derive parameters that are characteristic of the respective metal ion–donor bond types present. The parameterisation derived from the above (previously reported) stability data was then employed to compute log K values for the complexes of both the symmetrical and unsymmetrical ligand series. In general, quite good agreement with the experimentally determined log K values for both series of complexes was obtained. The procedure thus points the way for the prediction of metal complex stabilities for other systems that incorporate closely related ligand types.