ABSTRACT
Structures of LiSCN, NaSCN, KSCN, RbSCN, and CsSCN complexes with 3',5'-difluoro-4'-hydroxybenzyl-armed monoaza-15-crown-5 ether (5) were investigated. The Li+ and Na+ complexes are (1:1)n polymer-like complexes bridged by hydrogen bonding. On the other hand, the K+, Rb+, and Cs+ complexes are polymer-like complexes bridged by the fluorine atoms of the side arms. The titration calorimetry and 19F NMR titration experiments suggest that one or both fluorine atoms along with the oxygen atom of the phenolic OH group coordinate to the alkali metal ions incorporated in the crown part of a second armed ligand to give polymer-like complexes in solution. The FAB-MS data indicated that larger alkali metal ions form more stable polymer-like complexes.
ABSTRACT
A series of macrocyclic tetraazacrown ethers containing two pyridine, quinoline, 8-hydroxyquinoline, or 8-aminoquinoline sidearms has been prepared. Crab-like cyclization of bis(alpha-chloroacetamide)s and diamines followed by reduction of the cyclic diamides was used to synthesize the selected crown ethers containing two unsubstituted macroring nitrogen atoms. The preparation of the macrocycles with sidearms was accomplished by reductive amination of the proper aldehydes with the crown ethers using sodium triacetoxyborohydride (NaBH(OAc)(3)) as the reducing agent. The 8-hydroxyquinoline- and 8-aminoquinoline-containing macrocycles were synthesized by reductive amination of 8-acetoxyquinoline-2-carboxaldehyde or 8-nitroquinoline-2-carboxaldehyde followed by removing the acetate groups or reducing the nitro groups to amino groups, respectively. Complexation of ligand 22 with Cu(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), and Pb(2+) was evaluated potentiometrically in aqueous solution (0.10 M Me(4)NCl) at 25 degrees C. Ligand 22 formed very stable complexes with these metal ions. The UV-vis spectra of 22 and its complexes were examined in an aqueous acetic acid buffer solution (pH 5). The 22-Cu(2+) complex provided a new absorption band at 258 nm.
