Charge Distribution Dependent on the Chelating Ratio. [Co(μ-bpym)(dbbq)_2] vs. [{Co(dbbq)_2}_2(μ-bpym)] (bpym=2,2'-bipyrimidine; dbbq=3,6-di-t-butyl-1,2-benzoquinone)

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The preparation and characterization of [Co(<i>μ</i>-bpym)(dbbq)<sub>2</sub>] and [{Co(dbbq)<sub>2</sub>}<sub>2</sub>(<i>μ</i>-bpym)] (bpym = 2,2′-bipyrimidine; dbbq = 3,6-di-<i>t</i>-butyl-1,2-benzoquinone) have been established. The temperature-dependent magnetic moments (100—400 K) and variable-temperature near-infrared (NIR) absorption spectra are presented to show that the title complexes exhibit an equilibrium via a catechol to a cobalt intramolecular electron transfer. At temperatures below 200 K the mononuclear complex [Co(<i>μ</i>-bpym)(dbbq)<sub>2</sub>] has a charge distribution of [Co<sup>III</sup>(<i>μ</i>-bpym)(dbcat)(dbsq)] (dbsq = 3,6-di-<i>t</i>-butyl-1,2-semiquinonato; dbcat = 3,6-di-<i>t</i>-butylcatecholato), whereas at temperatures beyond 290 K the mononuclear complex is predominantly in the [Co<sup>II</sup>(<i>μ</i>-bpym)(dbsq)<sub>2</sub>] form. From 200—290 K a mixture of Co(III) and Co(II) redox isomers exists at equilibrium in the solid state. In particular, a thermal analysis of a solid sample of the mononuclear complex discloses that the transition for the Co(III)/Co(II) is accompanied by a change in the heat content of 36 kJ mol<sup>−1</sup>, which may be closely related to the band at 3878 cm<sup>−1</sup>, assigned as a dbcat to Co(III) charge transfer. In striking contrast, the dinuclear complex [{Co(dbbq)<sub>2</sub>}<sub>2</sub>(<i>μ</i>-bpym)] is locked in a charge distribution of [{Co<sup>II</sup>(dbsq)<sub>2</sub>}<sub>2</sub>(<i>μ</i>-bpym)] when the temperature is 100—400 K.

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  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 69(8), 2211-2214, 1996-08-15

    The Chemical Society of Japan

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  • NII論文ID(NAID)
    10008906968
  • NII書誌ID(NCID)
    AA00580132
  • 本文言語コード
    ENG
  • 資料種別
    ART
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    00092673
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    4060538
  • NDL 雑誌分類
    ZP1(科学技術--化学・化学工業)
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    Z53-B35
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    CJP書誌  NDL  J-STAGE 
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