Raman and infrared spectra of .MU.-O2 dicobalt(III) complexes.

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概要

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• Raman and infrared spectra of μ-hyperoxo and μ-peroxo ammine and cyano dicobalt(III) complexes have been studied and isotopic shifts of ν(OO) and ν(CoO) examined using <SUP>18</SUP>O. A μ-hyperoxo complex, [(NH<SUB>3</SUB>)<SUB>5</SUB>Co(O<SUB>2</SUB>)Co(NH<SUB>3</SUB>)<SUB>5</SUB>]X<SUB>5</SUB> shows peaks around 1110, 620, and 440 cm<SUP>−1</SUP> assignable to ν(OO), sν(CoO), and asν(CoO), respectively, whereas a μ-peroxo complex, [(NH<SUB>3</SUB>)<SUB>5</SUB>Co(O<SUB>2</SUB>)Co(NH<SUB>3</SUB>)<SUB>5</SUB>]X<SUB>4</SUB> shows peaks around 805, 645, and 545 cm<SUP>−1</SUP> assignable to ν(OO), sν(CoO), asν(CoO), respectively. These observed values are best reproduced, when the following force constants are assumed in the UBFF calculation: <I>K</I>(OO)=5.6, <I>K</I>(CoO)=1.40 mdyn/Å for μ-hyperoxo complexes and <I>K</I>(OO)=2.7, <I>K</I>(CoO)=2.15 mdyn/Å for μ-peroxo complexes. The calculated isotopic shifts are in good agreement with the observed ones. Raman and infrared spectra of dibridged μ-amido-μ-O<SUB>2</SUB> (both peroxo and hyperoxo) dicobalt(III) complex have also been characterized. A linear relationship has been found between ν(OO) and the bond order of the O<SUB>2</SUB> moiety in O<SUB>2</SUB>-complexes in different oxidation states including alkali hyperoxide, alkali peroxide, hydrogen peroxide, oxygen, and O<SUB>2</SUB><SUP>+</SUP> species.

• 公益社団法人 日本化学会の論文

著者

• Shibahara Takashi

  Department Of Chemistry Faculty Of Science Okayama University Of Science

• Mori Masayasu

  Department of Chemistry, Faculty of Science, Osaka City University

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