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Dithizonate (Hdz) and diphenylcarbazonate (Hdpc-)-chromium(III) complexes were extracted into basic solvent(B) as solvated ion-pairs, CrL(B)2(A)2 with counter anion(A-); where B=butyl acetate, isobutyl methyl ketone, isopentyl alcohol and trioctylphosphine oxide, and A=dodecyl sulfate ion(ds-). Anions having long chain alkyl groups, such as ds- and dodecylbenzenesulfonate ion, were effective for the extraction of the complexes, but tetraphenylborate ion and naphthalenesulfonate ion could not extract them. Ion-pair extraction constants, Kex=[CrL (ds-)2]. [CrL2+]-1[ds-]-2, between water and butyl acetate phase were 1010.70 and 1011.07 for L=Hdz- and Hdpc-, respectively (at I=-0.1, 20°C). Equilibrium constants, β2, for solvation of the ion-pairs in dichloromethane, β2=[CrL(B)2(ds-)2]0-1[B]0-2, were evaluated and a linear free energy relationship, log β2, Cr(Hdpc)2+=logβ2, Cr(Hdz)2++ 0.60, was, demonstrated. The difference in the Kex values between both chromium(III) complexes was discussed and mainly attributed to the difference in their β2 values.
- 公益社団法人 日本化学会の論文
公益社団法人 日本化学会 | 論文
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