Cation complexing properties of synthetic macrocyclic polyether-diester ligands containing the pyridine subcyclic unit

Journal Article · Wed Jan 16 04:00:00 EST 1980 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00522a004· OSTI ID:5241791

Bradshaw, J S; Maas, G E; Lamb, J D; Izatt, R M; Christensen, J J

Ten new macrocyclic polyether-diester compounds containing a pyridine subcyclic unit substituted in the 4 position with chloro or methoxy groups have been prepared. These compounds along with their unsubstituted pyridine analogues form strong complexes with alkylammonium and some metal cations. Complexation with alkylammonium and potassium cations was accompanied by significant chemical-shift changes in the /sup 1/H NMR spectra. Relative free energies of activation (..delta..G/sup not equal to/) for the dissociation of the alkylammonium complexes were determined from their temperature-dependent /sup 1/H NMR spectra. Complexes of the methoxy-substituted ligands with all the alkylammonium ions studied had a greater ..delta..G/sup not equal to/ than those of the chloro-substituted ligands. Formation constants as well as ..delta..H and T..delta..S values were determined by a calorimetric technique for the reaction of Na/sup +/, K/sup +/, Rb/sup +/, Ag/sup +/, NH/sub 4//sup +/, and Ba/sup 2 +/ with the ligands of 18 ring members containing pyridine and 4-chloropyridine subcyclic groups. The complexes formed between the alkali metal cations and these ligands were almost as stable as those formed with 18-crown-6 and pyridino-18-crown-6 (1). The pyridino ligands were also found to be effective carriers of Ag/sup +/ across a CHCl/sub 3/ liquid membrane separating aqueous phases.

• Research Organization: Brigham Young Univ., Provo, UT
• OSTI ID: 5241791
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102:2; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKALI METAL COMPLEXES
ALKALINE EARTH METAL COMPLEXES
ALKYL RADICALS
AMMONIUM COMPOUNDS
AZINES
BARIUM COMPLEXES
CHEMICAL PREPARATION
COMPLEXES
DATA
DATA FORMS
ESTERS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
ISOLATED VALUES
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
ORGANIC SULFUR COMPOUNDS
PHYSICAL PROPERTIES
POLYETHYLENE GLYCOLS
POLYMERS
POTASSIUM COMPLEXES
PYRIDINES
RADICALS
RUBIDIUM COMPLEXES
SILVER COMPLEXES
SODIUM COMPLEXES
SPECTRA
SYNTHESIS
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES