Dinuclear cobalt(II) complexes with various dinucleating ligands and their dioxygen complexes.
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概要
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Various types of dinuclear cobalt(II) complexes, [Co<SUB>2</SUB>L(CH<SUB>3</SUB>COO)<SUB>2</SUB>]ClO<SUB>4</SUB>, [Co<SUB>2</SUB>L(CH<SUB>3</SUB>COO)](ClO<SUB>4</SUB>)<SUB>2</SUB>, [CO<SUB>2</SUB>L(OH)](ClO<SUB>4</SUB>)<SUB>2</SUB>, [Co<SUB>2</SUB>L(C<SUB>3</SUB>H<SUB>3</SUB>N<SUB>2</SUB>)]ClO<SUB>4</SUB>)<SUB>2</SUB>(C<SUB>3</SUB>H<SUB>3</SUB>N<SUB>2</SUB><SUP>−</SUP>)=pyrazolate), and [CO<SUB>2</SUB>LX<SUB>2</SUB>](ClO<SUB>4</SUB>)<I><SUB>n</SUB></I>, were prepared, where HL represents 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol(Hbpmp), 2,6-bis[<I>N</I>-(2-pyridylmethyl)-2-(2-pyridyl)ethylaminomethyl]-4-methylphenol(Hbpmep), 2,6-bis[bis[2-(2-pyridyl)ethyl]aminomethyl]-4-methylphenol(Hbpmep), and 2,6-bis[bis(2-benzirnidazolylmethyl)aminometnyl]-4-metnylphenol(Hbbimp), and X is N<SUB>3</SUB><SUP>−</SUP>, NCS<SUP>−</SUP>, Cl<SUP>−</SUP>, Br<SUP>−</SUP>, H<SUB>2</SUB>O, or py(pyridine). The electronic spectra and magnetic moments of the complexes revealed that [Co<SUB>2</SUB>L(CH<SUB>3</SUB>COO)<SUB>2</SUB>]ClO<SUB>4</SUB> (L=bpmp, bpmep, or bpep) are high-spin octahedral, whereas the other complexes have five-coordinate structure of high-spin configuration. Some of the bpmp and the bpmep complexes reacted reversibly with molecular oxygen more or less. The <I>P</I><SUB>1⁄2</SUB> of some complexes were determined spectrometrically. The oxygen affinities of the complexes are highly dependent on the natures of the dinucleating ligands and additional bridging or unidentate ligands.
- 公益社団法人 日本化学会の論文
著者
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KANATOMI Hajime
Laboratory of Chemistry, College of General Education, Kyushu University
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Suzuki Masatatsu
Laboratory of Chemistry, College of General Education, Kyushu University
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Murase Ichiro
Laboratory of Chemistry, College of General Education, Kyushu University
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