Accelerating effect of donor solvents on racemization of the tris(1,10-phenanthroline)iron(II) cation.
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概要
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Rates of racemization of the tris(1,10-phenanthroline)iron(II) cation, [Fe(phen)<SUB>3</SUB>]<SUP>2+</SUP>, have been measured at 7.5 °C to 17.5 °C in 1,2-dichloroethane, <I>o</I>-dichlorobenzene, nitrobenzene, and nitromethane, and in 1,2-dichloroethane solutions containing dimethyl sulfoxide (DMSO), <I>N</I>,<I>N</I>-dimethylformamide (DMF), methanol (MeOH), acetone (Ac), and acetonitrile (AN). In the four pure solvents, the observed racemization rates are markedly smaller than those calculated by the Van Meter and Neumann equation, which relates the racemization rate to the solvation energy of the phen ligands and viscous resistance. Addition of donor solvents to 1,2-dichloroethane solutions of the iron complex enhances the racemization rates. The degree of enhancement increases in the order AN<Ac<MeOH<DMF<DMSO and the activation energy decreases in the same order. This sequence lies in the order of increasing Gutmann donor number of the solvents, indicating a nucleophilic interaction of the solvents with the iron metal in the transition state. These obsevations may be interpreted in terms of Kepert' s model for solvent-assisted racemization of tris-chelated complexes and the molecular structure of a solvate complex determined previously, and allow us to modify the Van Meter and Neumann equation.
- 公益社団法人 日本化学会の論文
著者
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Fujiwara Terufumi
Department Of Chemistry Graduate School Of Science Hiroshima University
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Okamoto Yoshiharu
Department of Chemistry, Faculty of Science, Hiroshima University
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Yamamoto Yuroku
Environmental and Safety Engineering Department, Fukui Institute of Technology
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