ANION COORDINATION CHEMISTRY - POLYGUANIDINIUM SALTS AS ANION COMPLEXONES

The synthesis of a series of polyguanidinium salts of potential interest as anion complexones is described. Among the various synthetic methods investigated, the polyguanidinium salts were found to be most conveniently prepared from polyamines via polynitroguanidine intermediates. The complexation of phosphate and carboxylate anions by these complexones and by related polyammonium salts were studied by analysis of pH‐metric titration data. The ligands studied from relatively stable complexes (log Ks = 2.0–4.0 for PO 43− in water) which also present good selectivities in some cases. Both the stability and the selectivity of complexation are primarily governed by electrostatic forces and thus depend on charge accumulation in the interacting species; structural effects are also observed. Since the binding is primarily electrostatic, polyammonium salts from more stable complexes (at a given charge) than do polyguanidinium salts. However, whereas the complexation properties of the latter are independent of pH, the complexes of the former are observed only in the limited ranges of pH where both the protonated polyamine and the anion of interest can coexist. The polycationic ligands may, in principle, form chelate type anion complexes. Comparison with the corresponding single binding sites reveals an increase in complexation constant of about two or three orders of magnitude; this may be considered as a thermodynamic indication of a chelate effect for the polydentate ligands (by analogy with the well known effects displayed by cation complexones); however, structural data on the formation of chelate ‘rings’ are not yet available. The nature of the complexes and the prospects of anion complexones in various fields are discussed. Copyright © 1979 Verlag GmbH & Co. KGaA, Weinheim