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A Conductance Study of 1:1 Complexes of 15-Crown-5, 16-Crown-5, and Benzo-15-crown with Alkali Metal Ions
Conductivities of alkali metal salts in the presence of 15-crown-5 (15C5), 16-crown-5 (16C5), and benzo-15-crown-5 (B15C5) were measured at 25 deg C in acetonitrile, propylene carbonate, and methanol.Formation constants (KML+) of 1:1 complexes of 15C5 and 16C5 with alkali metal ions and conductance parameters (lambda0 and a0) of the Na+ complexes of 15C5, 16C5, and B15C5 were determined, lambda0 and a0 being limiting ionic molar conductivity and distance of closest approach of ions, respectively.In general, selectivities of 15C5 and 16C5 for alkali metal ions show the size-fit correlation.In contrast to 15C5, 16C5 forms much the most stable complex with Na+ in every solvent.Generally, KML+-value sequences of a given crown ether complex for the solvents are the reverse of donor-number sequences of the solvents.Value of a0 increases with an increase in the cationic size (Na+->Na(15C5)+->Na(16C5)+->Na(B15C5)+).Mobility of the Na+-crown ether complex decreases with an increase in the size of the crown ether.From lambda0 values and Walden products of these Na(crown ether)+ complexes and a tetrapropylammonium ion, it seems likely that Na(15C5)+ and Na(16C5)+ act as structure breakers in hydrogen-bonding solvents, whereas Na(B15C5)+ as a structure maker.
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Chiral Catalysts,
Chiral catalysts – SlideShare