Substituent group electronic effects on inversion and proton-exchange rates at chiral nitrogen centers for a series of bis(.BETA.-diketonato)-(N-methylethylenediamine)cobalt(III) complexes.

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概要

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• The rates of the base-catalyzed proton exchange (deuteration, <I>k</I><SUB>D</SUB>) and inversion (epimerization, <I>k</I><SUB>ep</SUB>) at chiral nitrogen centers of [Co(Xacac)<SUB>2</SUB>(Me-en)]<SUP>+</SUP> (Xacac: NO<SUB>2</SUB>acac=3-nitro-2,4-pentanedionate, Clacac=3-chloro-2,4-pentanedionate, CH<SUB>3</SUB>acac=3-methyl-2,4-pentanedionate; Me-en=<I>N</I>-methylethylenediamine) in aqueous solutions have been measured at 34.0 °C, and the results were compared with one another and with those of the corresponding acac complex (acac=2,4-pentanedionate) in order to investigate the substituent influence on the rates. The <I>k</I><SUB>D</SUB> and <I>k</I><SUB>ep</SUB> values of the NO<SUB>2</SUB>acac complex are ca. 10<SUP>4</SUP> and ca. 10<SUP>6</SUP> times, respectively, larger than those of the CH<SUB>3</SUB>acac complex. The effect of substituents is electronic and the Hammett relationship was found to hold for both deuteration and epimerization rates. The reduction (Co<SUP>3+</SUP>/Co<SUP>2+</SUP>) half-wave potential, <I>E</I><SUB>1⁄2</SUB> obtained by rotating glassy carbon electrode voltammetry increases from −0.59 V (vs. SCE) for the CH<SUB>3</SUB>acac complex to −0.08 V for the NO<SUB>2</SUB>acac complex. A linear dependence was observed between <I>E</I><SUB>1⁄2</SUB> and the Hammett parameter.

• 公益社団法人 日本化学会の論文

著者

• Kojima Masaaki

  Department Of Chemistry Faculty Of Science Okayama University

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Ma Guilin

  Department of Chemistry, Faculty of Science, Nagoya University

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