AbstractIt is shown that the stability constants of the silver complexes with various diamines, triamines and tetramines can be predicted in most cases quantitatively with the simple assumption of the existence of two opposite coordination points on the silver cation only, using the well known relation betweenKAgA,KAg2AandKHA, the formation constants of the silver and proton complexes with simple monoamines. Out of a number of 29 complex ions, comprising the dimeric form of Ag(en), the stability of 24 could be calculated correctly. In two cases, where the amino group adding the silver is strongly influenced by a nearby ionic charge on the molecule, the calculated values were too large. For three other complexes, containing all more than two amino groups per Ag, the theoretically calculated values were somewhat too small, indicating in these cases the coordination of more than two basic nitrogen atoms by the silver cation.