1,4,8,11-テトラメチル-1,4,8,11-テトラアザシクロテトラデカンニッケル(II)をプローブとして用いた水の分極と酸性度-塩基性度の研究

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The effects of charge transfer through hydrogen-bonding and coordination on the acidity-basicity of water molecules in various mixed organic solvents including a reversed micellar medium were investigated spectrophotometrically using 1R, 4S, 8R, 11S-Tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) ([Ni(tmc)]^<2+>) as a probe for the axial coordination of water. In the mixed organic solvent system the coordination ability (basicity) of the water (W) which is hydrogen-bonded to a donor solvent (S) as a 1 : 1 complex (WS) is increased with increasing the basicity of S. The residual hydrogen atom of the coordinated water in [Ni(tmc) (WS)]^<2+> can be hydrogen-bonded to further species such as S and WS to form additional kinds of five-coordinated complexes. The hydrogen-bonding ability (acidity) of the residual hydrogen atom of the water is also increased with increasing the basicity of S, showing that the synergism of hydrogen-bonding and coordination works efficiently. In the reversed micelle system for a water-to-AOT (sodium bis(2-ethyl-1-hexyl)sulfosuccinate) molar ratio (R) of above 10 the spectrum of [Ni(tmc)]^<2+> is very similar to that in bulk water, but below R=10 the peaks of the five-coordinated complex shift to longer wavelengths and at R=1 the spectrum is very similar to that of the hydroxide ion-coordinated complex. This shows that a decrease in the R value obviously leads to a gradual increase in the polarization of water coordinated to [Ni(tmc)]^<2+> owing to the cooperative influence of the sulfo ion of AOT and [Ni(tmc)]^<2+> through hydrogen bonding at the water-surfactant interface. It was concluded that the cooperative interaction through hydrogen-bonding plays an important role in the basicity and acidity of water.
社団法人日本分析化学会の論文
1994-05-05

著者

西本潤
佐賀大学理工学部化学科

1,4,8,11-テトラメチル-1,4,8,11-テトラアザシクロテトラデカンニッケル(II)をプローブとして用いた水の分極と酸性度-塩基性度の研究

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