Association of Tris(acetylacetonato)chromium(III) with Chlorinated Phenols in the Liquid-Liquid Partition System.

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概要

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• The liquid–liquid partition behavior of tris(acetylacetonato)chromium(III) ([Cr(acac)3]) between heptane and 0.10 mol dm<SUP>−3</SUP> aqueous sodium perchlorate solutions has been studied in the presence of a series of chlorinated phenols (HA) at 298.2 K. A large enhancement of the partition coefficient of [Cr(acac)<SUB>3</SUB>] with HA has been observed, e.g., it rises by about 1000-fold in the presence of 0.02 mol dm<SUP>−3</SUP> 3,5-dichlorophenol in the organic phase. This effect is ascribable to the association of [Cr(acac)<SUB>3</SUB>] with HA in the organic phase. From a partition-equilibrium analysis, the association complexes have been identified as being [Cr(acac)<SUB>3</SUB>]·<I>i</I>HA (<I>i</I>=1,2), and the association constants (β<SUB>ass,<I>i</I></SUB>) determined. The β<SUB>ass,<I>i</I></SUB>, value increases with an increase of the acid-dissociation constant of HA in the family of HA with the same combination of substituents at the 2,6-positions, i.e., the association is due to hydrogen bonding of the hydroxyl hydrogen atom of HA to [Cr(acac)<SUB>3</SUB>]. A linear free-energy relationship has been found between the β<SUB>ass,<I>i</I></SUB>, values of [Cr(acac)<SUB>3</SUB>] and those of [Co(acac)<SUB>3</SUB>] previously reported.

• 公益社団法人 日本化学会の論文

著者

• Katsuta Shoichi

  Department Of Chemistry Faculty Of Science Chiba University

• Suzuki Nobuo

  Department Of Applied Physics Faculty Of Engineering Tohoku University

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