Triple ion and quadrupole formations from trialkylammonium sulfonates and nitrate in protophobic aprotic solvents with higher dielectric constants.
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概要
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The formation of symmetrical triple ions (2M<SUP>+</SUP>+X<SUP>−</SUP>\rightleftarrowsM<SUB>2</SUB>X<SUP>+</SUP>, (<I>K</I><SUB>2</SUB>); M<SUP>+</SUP>+2X<SUP>−</SUP>\rightleftarrowsMX<SUB>2</SUB><SUP>−</SUP>, (<I>K</I><SUB>3</SUB>); <I>K</I><SUB>2</SUB>=<I>K</I><SUB>3</SUB>) and the quadrupole (M<SUB>2</SUB>X<SUP>+</SUP>+X<SUP>−</SUP>\rightleftarrowsM<SUB>2</SUB>X<SUB>2</SUB>, (<I>K</I><SUB>4</SUB>); MX<SUB>2</SUB><SUP>−</SUP>+M<SUP>+</SUP>\rightleftarrowsM<SUB>2</SUB>X<SUB>2</SUB>, (<I>K</I><SUB>5</SUB>); <I>K</I><SUB>4</SUB>=<I>K</I><SUB>5</SUB>), in addition to the ion pair formation (M<SUP>+</SUP>+X<SUP>−</SUP>\rightleftarrowsMX, (<I>K</I><SUB>1</SUB>)) from uni-univalent salts (MX) has been examined in acetonitrile (dielectric constant ε=35.95), benzonitrile (ε=25.2), nitrobenzene (ε=34.82), and nitromethane (ε=36.67) at 25° by means of conductometry. Tho molar conductivities (<I>Λ</I>) of tributylammonium methanesulfonate (<I>n</I>-Bu<SUB>3</SUB>NHCH<SUB>3</SUB>SO<SUB>3</SUB>) of (0.4–6.0) ×10<SUP>−3</SUP>M (1 M=1 mol dm<SUP>−3</SUP>) in benzonitrile were explained by the formation of triple ions (<I>K</I><SUP>a</SUP><SUB>1</SUB>=8.4×10<SUP>4</SUP>, <I>K</I><SUP>a</SUP><SUB>2</SUB>=<I>K</I><SUP>a</SUP><SUB>3</SUB>=5.5×10<SUP>5</SUP>, corrected by the activity coefficients of ions) within ±0.85% relative error, assuming that <I>Λ</I><SUB>T</SUB>=<I>Λ</I><SUB>O</SUB>⁄3 (<I>Λ</I><SUB>T</SUB>: the limiting molar conductivity of the triple ions; <I>Λ</I><SUB>O</SUB>: that of the simiple ions). In nitrobenzene, however, the quadrupole formation must be invoked for the salt in the same concentration range (<I>K</I><SUP>a</SUP><SUB>1</SUB>=1.38×10<SUP>5</SUP>, <I>K</I><SUP>a</SUP><SUB>2</SUB>=<I>K</I><SUP>a</SUP><SUB>3</SUB>=4.75×10<SUP>7</SUP>, <I>K</I><SUP>a</SUP><SUB>4</SUB>=<I>K</I><SUP>a</SUP><SUB>5</SUB>=8.5×10<SUP>2</SUP>). The alternative formation constant of the quadrupole (2MX\rightleftarrowsM<SUB>2</SUB>X<SUB>2</SUB>, (<I>K</I><SUB>41</SUB>)) was evaluated as <I>K</I><SUP>a</SUP><SUB>41</SUB>=5.0 instead of <I>K</I><SUP>a</SUP><SUB>4</SUB>. Triple ion formation was observed in acetonitrile and nitromethane, but not in an amphiprotic solvent, ethanol (ε=24.55). The tendency for triple ion formation or higher aggregate formations from trialkylammonium salts was found to decrease as follows: Cl<SUP>−</SUP>>CH<SUB>3</SUB>SO<SUB>3</SUB><SUP>−</SUP>, Br<SUP>−</SUP>> TsO<SUP>−</SUP>, NO<SUB>3</SUB><SUP>−</SUP>>I<SUP>−</SUP>, CF<SUB>3</SUB>SO<SUB>3</SUB><SUP>−</SUP>> (ClO<SUB>4</SUB><SUP>−</SUP>). The difference in the aggregate forming ability is discussed from the view point of basicity of the anions, the strength for a proton acceptor in hydrogen bonding, and the localization of electrons in the anion molecule.
著者
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Imai Yoshihiko
Department Of Applied Physics University Of Tokyo
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Hojo Masashi
Department Of Chemistry Faculty Of Science Kochi University
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Miyauchi Yoshihiro
Department of Chemistry, Faculty of Science, Kochi University
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