Access to the enthalpy and entropy of the formation of metal complexes in solution is essential for understanding the factors determining their thermodynamic stability and speciation. As a case study, in this report we systematically examine the complexation of silver(I) in acetonitrile (AN) with the following monoamines: n-propylamine (n-pr), n-butylamine (n-but), hexylamine (hexyl), diethylamine (di-et), dipropylamine (di-pr), dibutylamine (di-but), triethylamine (tri-et) and tripropylamine (tri-pr). The study shows that the complex stabilities are quite independent of the length of the substitution chain on the N atom and demonstrates that, in general, the overall enthalpy terms associated with the complex formation are strongly exothermic, whereas the entropy values oppose the complex formations. In addition, we examined the similarity of the formation constants of AgL complexes of the primary monoamines in AN, dimethylsulfoxide (DMSO) and water, which were unexpected on the basis of the difference between the donor properties of solvents.
