A conductance study of 1:1 complexes of 15-crown-5, 16-crown-5, and benzo-15-crown-5 with alkali metal ions in nonaqueous solvents.

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概要

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• 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 °C in acetonitrile, propylene carbonate, and methanol. Formation constants (<I>K</I><SUB>ML<SUP>+</SUP></SUB>) of 1:1 complexes of 15C5 and 16C5 with alkali metal ions and conductance parameters (λ<SUP>0</SUP> and å) of the Na<SUP>+</SUP> complexes of 15C5, 16C5, and B15C5 were determined, λ<SUP>0</SUP> and å 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<SUP>+</SUP> in every solvent. Generally, <I>K</I><SUB>ML<SUP>+</SUP></SUB>-value sequences of a given crown ether complex for the solvents are the reverse of donor-number sequences of the solvents. Value of å increases with an increase in the cationic size (Na<SUP>+</SUP>→Na(15C5)<SUP>+</SUP>→Na(16C5)<SUP>+</SUP>→Na(B15C5)<SUP>+</SUP>). Mobility of the Na<SUP>+</SUP>–crown ether complex decreases with an increase in the size of the crown ether. From λ<SUP>0</SUP> values and Walden products of these Na(crown ether)<SUP>+</SUP> complexes and a tetrapropylammonium ion, it seems likely that Na(15C5)<SUP>+</SUP> and Na(16C5)<SUP>+</SUP> act as structure breakers in hydrogen-bonding solvents, whereas Na(B15C5)<SUP>+</SUP> as a structure maker.

• 公益社団法人 日本化学会の論文

著者

• Takeda Yasuyuki

  Department Of Chemistry Faculty Of Science Chiba University

• HAKUSHI Tadao

  Department of Applied Chemistry, Faculty of Engineering, Himeji Institute of Technology

• Inoue Yoshihisa

  Basic Research Laboratory, Himeji Institute of Technology

• Katsuta Koji

  Department of Chemistry, Faculty of Science, Chiba University

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