UNUSUAL REACTIONS OF THE HIGHLY STRAINED MACROCYCLES WITH LITHIUM SALTS: ANION CONTROL FOR THE REACTION RATES AND ELUCIDATION OF THE PROPERTIES OF THEIR LITHIUM COMPLEXES

摘要

The complexation reactions of dicyano monoalkyl tetraaz macrocycle 3b with lithium salts (Li~+X~-) and the properties of resulting macrocycle 3b-Li~+X~- complexes were examined in detail by means of ~1H-NMR spectroscopy, because unsymmetrical macrocycle 3b has exhibited intriguing features, such as high selectivity for binding to the Li~+ ion. The following noticeable facts were found; the reaction rates of complexation are heavily controlled by the properties of anion (X~-) and the spectroscopic properties of macrocycle 3b-Li~+ X~- complexes are also changed by the anion. The major origin for the unusual Li~+ complexation reactions and the specific behavior of Li~+ complexes would come from the unique properties of metal free macrocycle 3b, because macrocycle 3b has a strong intramolecular hydrogen bond in the macrocyclic ring and the highly strained macrocyclic ring by unsymmetrical structure consisting of nonplanar and planar moieties.