冠醚与己二胺盐酸盐作用的热力学数据.pdfVIP

J Solution Chem (2008) 37: 595–601 DOI 10.1007/s10953-008-9263-5 Thermodynamic Data for the Formation of 1:1 and 2:1 Complexes of α,ω-Diamino Dihydrochlorides with 18-Crown-6 in Aqueous Solution Mirac Ocak · Hans-Jürgen Buschmann · Eckhard Schollmeyer Received: 23 April 2007 / Accepted: 4 October 2007 / Published online: 6 March 2008 © Springer Science+Business Media, LLC 2008 Abstract Calorimetric titrations are used to study the interactions between the crown ether 18-crown-6 and several α,ω-diamino dihydrochlorides in aqueous solution. These com- plexes are formed by ion-dipole interactions between the positively charged nitrogen atoms and the oxygen donor atoms of the crown ether. Depending on the experimental conditions, the formation of 1:1 or 2:1 complexes (ligand:diamines) can be studied. The solvation of the ligand and the amines are responsible for the observed thermodynamic values. The number of water molecules released during the reaction were calculated from the determined reac- tion entropies. Formation of 1:1 complexes distorts the solvation shell around the molecules. As a result, the number of solvent molecules released during the formation of the 2:1 com- plexes is slightly smaller than the number released from formation of the 1:1 complex. No experimental evidence is observed for the formation of complexes between one crown ether and two protonated amino groups. Keywords Stability constants · Solvation · Thermodynamic data · Diamines · 18-Crown-6 complex formation 1 Introduction During the last two decades, supramolecular chemistry [ 1–3] has been established as an important new chemical field. In 1967, Pedersen described the first synthetic macrocyclic ligands [4]. He called them crown ethers due to their structures. These macrocyclic ligands were the first neutral synthetic compounds capable of complexing alkali metal cations [4, 5]. The complex stability for a given alkali metal cation depends on the r