Abstract
The complex formation of Ag + with a variety of noncyclic ligands, crown ethers, aza crown ethers and cryptands has been studied in methanol by potentiometric and calorimetric titration. From the measured reaction enthalpies with different noncyclic ligands it is deduced that the bond strength between the silver ion and different donor atoms decrease in the order: N > S > O. A macrocyclic effects for ligands containing only oxygen as donor atoms was found, caused by a favourable entropic change. Complexes of aza crowns and their non-cyclic analogues have the same stabilities. The existence of different conformations of the cyclic ligands is mainly responsible for the absence of the macrocyclic effect. A cryptate effect for the complexation of Ag + was observed, due to an increase in Δ H.
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