Stability constants, enthalpies, and entropies for metal ion-lariat ether interactions in methanol solution

Journal Article · Fri Dec 28 00:00:00 EST 1984 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00200a011· OSTI ID:5768285

Davidson, R B; Izatt, R M; Christensen, J J; Schultz, R A; Dishong, D M; Gokel, G W

Log K/sub n/, ..delta..H/sub n/, and T..delta..S/sub n/ values valid in CH/sub 3/OH at 25/sup 0/C have been determined for the interaction of Na/sup +/, K/sup +/, Cs/sup +/, and Ca/sup 2 +/ with 15-crown-5 and several lariat ethers. The lariat ethers studied are based on both 15-crown-5 and 18-crown-6 frameworks and contain various pendant arms extending from either carbon or nitrogen atoms on the crown framework. In comparable cases, enlarging the ring size from 15 to 18 members resulted in increased stability. The inclusion on the aza-15-crown-5 ring of a pendant arm bound to nitrogen and having an oxygen atom in the 3 position increases complex stability. The inclusion on the aza-15-crown-5 ring of a pendant arm bound to nitrogen and having an oxygen atom in the 3 position increases complex stability about ten-fold for Na/sup +/, K/sup +/, and Ca/sup 2 +/ compared to the crown ether with the same ring structure but lacking a heteroatom in the side arm. Generally, little effect on the log K/sub n/ value is found either by lengthening the pendant arm (and by including an additional donor atom) on the 18-crown-6 compounds or by appending pendant arms having oxygen atoms on the carbon pivot atom of the 15-crown-5 macrocycles. 25 references, 1 figure, 2 tables.

• Research Organization: Brigham Young Univ., Provo, UT
• DOE Contract Number: AC02-78ER05016
• OSTI ID: 5768285
• Journal Information: J. Org. Chem.; (United States), Vol. 49:26
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CALCIUM COMPOUNDS
COMPLEXOMETRY
CESIUM COMPOUNDS
POLYETHYLENE GLYCOLS
POTASSIUM COMPOUNDS
SODIUM COMPOUNDS
AZO COMPOUNDS
CALORIMETRY
CATIONS
CHEMICAL ANALYSIS
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
DATA ACQUISITION
DATA ANALYSIS
ENTHALPY
ENTROPY
EXPERIMENTAL DATA
METHANOL
ORGANIC SOLVENTS
PROGRAMMING
STOICHIOMETRY
THERMODYNAMICS
ALCOHOLS
ALKALI METAL COMPOUNDS
ALKALINE EARTH METAL COMPOUNDS
CHARGED PARTICLES
DATA
GLYCOLS
HYDROXY COMPOUNDS
INFORMATION
IONS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
PHYSICAL PROPERTIES
POLYMERS
SOLVENTS
THERMODYNAMIC PROPERTIES
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)