Cation-complexing properties of synthetic macrocyclic polyether-diester ligands containing the furan, benzene, tetrahydrofuran, and thiophene subcyclic units

Journal Article · Wed Apr 08 04:00:00 EST 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00397a041· OSTI ID:6395282

Bradshaw, J S; Baxter, S L; Lamb, J D; Izatt, R M; Christensen, J J

The synthesis of 13 new macrocyclic polyether-diester ligands containing the furan, 3,4-dimethoxyfuran, tetrahydrofuran, and thiophene subcyclic by the reaction of a diacid dichloride with the appropriate glycol is described. The complexation properties of these ligands with alkylammonium and metal cations were determined and compared with the crown ethers. The free energies of activation (..delta..G*) for the dissociation of the alkylammonium complexes were determined from their temperature-dependent /sup 1/H NMR spectra. The relative kinetic stability (as measured by the ..delta..G* values) for the complexes between benzylammonium perchlorate and ligands containing an aromatic subcyclic unit increased with increasing ring size in the order 18-<21-<24-membered ring. Formation constants as well as ..delta..H and T..delta..S values were determined in methanol by a calorimetric titration technique for the reaction of Na/sup +/, K/sup +/, Cs/sup +/ and Sr/sup 2 +/ with the tetrahydrofurano ligands. The 21- and 24-membered ring compounds containing a furan subcyclic unit were found to be effective carriers of Cs/sup +/ across a CHC1/sub 3/ ligand membrane separating aqueous phases.

• Research Organization: Brigham Young Univ., Provo, UT
• OSTI ID: 6395282
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:7; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400105 -- Separation Procedures
400301* -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
ALCOHOLS
ALKALI METAL COMPLEXES
AQUEOUS SOLUTIONS
AROMATICS
BENZENE
CESIUM COMPLEXES
CHARGED PARTICLES
CHEMICAL PREPARATION
COMPLEXES
DATA
DISPERSIONS
ESTERS
EXPERIMENTAL DATA
FURANS
GLYCOLS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROXY COMPOUNDS
INFORMATION
IONS
MEMBRANE TRANSPORT
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC POLYMERS
ORGANIC SULFUR COMPOUNDS
POLYETHYLENE GLYCOLS
POLYMERS
SOLUTIONS
SYNTHESIS
TETRAHYDROFURAN
THIOPHENE