Bridges in polynuclear complexes. I. The reaction and reaction products of .MU.(NH2,O2) dicobalt complexes with nitrites.
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概要
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The IR spectroscopy of the μ-amido-μ-nitro complex, [(NH<SUB>2</SUB>,N0<SUB>2</SUB>){Co(NH<SUB>3</SUB>)<SUB>4</SUB>}<SUB>2</SUB>]Cl<SUB>4</SUB>·2H<SUB>2</SUB>O obtained from normal and <SUP>18</SUP>O-labeled [(NH<SUB>2</SUB>,O<SUB>2</SUB>){Co(NH<SUB>3</SUB>)<SUB>4</SUB>}<SUB>2</SUB>](NO<SUB>3</SUB>)<SUB>4</SUB> has revealed that the O atom in the Co–N–O–Co chain comes from the O<SUB>2</SUB> bridge of the starting complex, whereas the O atom attached to the N atom from outside the chain comes from the nitrite used in the bridge conversion, μO<SUB>2</SUB>→μNO<SUB>2</SUB>. A reaction mechanism involving N<SUB>2</SUB>O<SUB>3</SUB> as the reacting species is proposed. The reaction of [(NH<SUB>2</SUB>,O<SUB>2</SUB>){Co(NH<SUB>3</SUB>)<SUB>4</SUB>}<SUB>2</SUB>]X<SUB>3</SUB> with the nitrite in neutral solution gave a non-electrolytic μ-hyperoxo dicobalt complex, [(NH<SUB>2</SUB>,O<SUB>2</SUB>)Co<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB>(NO<SUB>2</SUB>)<SUB>4</SUB>](I). Treatment of I with perchloric acid gave a triple-bridged complex, [(NH<SUB>2</SUB>,NO<SUB>2</SUB>,O<SUB>2</SUB>)Co<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB>(NO<SUB>2</SUB>)<SUB>2</SUB>]<SUP>+</SUP>, which reproduces I when treated with sodium nitrite.
- 公益社団法人 日本化学会の論文
著者
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Shibahara Takashi
Department Of Chemistry Faculty Of Science Okayama University Of Science
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Mori Masayasu
Department of Chemistry, Faculty of Science, Osaka City University
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Kubo Shigekazu
Department of Chemistry, Faculty of Science, Osaka City University
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Shibahara Takashi
Department of Chemistry, Faculty of Science, Osaka City University
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