Heats of protonation of amines, diazacrown ethers and cryptands in methanol

Abstract

The heats of protonation of different amines, diazacrown ethers and cryptands in methanol have been measured using calorimetric titrations. The values of the reaction enthalpies decrease in going from primary over secondary to tertiary amines. The results for the protonation of diazacrown ethers and cryptands are not comparable with those obtained for the alkyl amines. Additional interactions between the proton and the oxygen donor atoms influence the values of the reaction enthalpy for the first protonation. The results for the second protonation reaction indicate that this proton is located outside the cavities of the macrocyclic and macrobicyclic ligands.