The Reaction and Reaction Products of μ-O<SUB>2</SUB>-Dicobalt Ammine Complexes with Nitrites, Thiocyanates, <I>etc</I>.
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概要
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In a neutral solution [NH<SUB>3</SUB>(en)<SUB>2</SUB>CoO<SUB>2</SUB>Co(en)<SUB>2</SUB>NH<SUB>3</SUB>]<SUP>4+</SUP> was found to react with NO<SUB>2</SUB><SUP>−</SUP> and SCN<SUP>−</SUP> to give [NO<SUB>2</SUB>-(en)<SUB>2</SUB>CoO<SUB>2</SUB>Co(en)<SUB>2</SUB>NO<SUB>2</SUB>]<SUP>2+</SUP> and [SCN(en)<SUB>2</SUB>CoO<SUB>2</SUB>Co(en)<SUB>2</SUB>NCS]<SUP>2+</SUP> respectively, without causing any cleavage of the O<SUB>2</SUB>-bridge, while in an acid solution it was found to be oxidized by NO<SUB>2</SUB><SUP>−</SUP> to a μ-superoxo (O<SUB>2</SUB><SUP>−</SUP>) complex ion, [NH<SUB>3</SUB>-(en)<SUB>2</SUB>CoO<SUB>2</SUB>Co(en)<SUB>2</SUB>NH<SUB>3</SUB>]<SUP>5+</SUP>. The latter is not affected by NO<SUB>2</SUB><SUP>−</SUP>, in contrast with [(en)<SUB>2</SUB>Co(μ-NH<SUB>2</SUB>,O<SUB>2</SUB>)Co(en)<SUB>2</SUB>]<SUP>4+</SUP>, in which the O<SUB>2</SUB><SUP>−</SUP>-bridge is replaced by an NO<SUB>2</SUB><SUP>−</SUP>-bridge. The [NO<SUB>2</SUB>(en)<SUB>2</SUB>CoO<SUB>2</SUB>Co(en)<SUB>2</SUB>NO<SUB>2</SUB>]<SUP>2+</SUP> formed as described reacts with CN<SUP>−</SUP> to give [Co<SUB>2</SUB>(CN)<SUB>6</SUB>(en)<SUB>2</SUB>O<SUB>2</SUB>]<SUP>2−</SUP>. The EPR spectra of some new μ-superoxo complexes which were synthesized by oxidizing some of the above μ-peroxo complexes were measured and compared with those of similar complexes. Infrared and electronic spectra were also taken.
- 公益社団法人 日本化学会の論文
著者
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Mori Masayasu
Faculty of Science Osaka City University
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Mori Masayasu
Faculty of Science, Osaka City University
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Shibahara Takashi
Faculty of Science, Osaka City University
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