Dinuclear cobalt(II) complexes containing 1,3-(or 1,5-)bis(bis(2-pyridylmethyl)amino)-2-propanolato(or -3-pentanolato): Preparation and reaction with molecular oxygen.
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概要
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Two dinuclear cobalt(II,II) complexes, [Co<SUB>2</SUB>(tpdp)(CH<SUB>3</SUB>COO)](ClO<SUB>4</SUB>)<SUB>2</SUB>·0.5H<SUB>2</SUB>O (<B>1</B>) and [Co<SUB>2</SUB>(tmdp)(CH<SUB>3</SUB>COO)](ClO<SUB>4</SUB>)<SUB>2</SUB>·H<SUB>2</SUB>O (<B>2</B>), were prepared, where Htpdp and Htmdp are 1,3-bis[bis(2-pyridylmethyl)amino]-2-propanol and 1,5-bis[bis(2-pyridylmethyl)amino]-3-pentanol respectively. Their electronic spectral and magnetic data revealed that <B>1</B> and <B>2</B> are five-coordinate in the high-spin state, in the same manner as [Co<SUB>2</SUB>(bpmp)(CH<SUB>3</SUB>COO)]<SUP>2+</SUP> (<B>3</B>) (Hbpmp=2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol). The complexes reacted with molecular oxygen to form μ-peroxo complexes in dichloromethane and acetonitrile. The oxygen affinity of the complexes decreased in the order of <B>3</B>><B>2</B>><B>1</B>. The relationships between the oxygen affinities and (1) the donor abilities of dinucleating ligands, (2) the energies of the charge-transfer bands (O<SUB>2</SUB><SUP>2−</SUP> to Co<SUP>3+</SUP>) of the μ-peroxo complexes, and (3) the redox potentials of the Co<SUP>3+</SUP>–O<SUB>2</SUB><SUP>−</SUP>–Co<SUP>3+</SUP>/Co<SUP>3+</SUP>–O<SUB>2</SUB><SUP>2−</SUP>–Co<SUP>3+</SUP> couple indicated that a steric effect arising from the dinucleating ligands contributes significantly to the oxygen affinities of the complexes.
- 公益社団法人 日本化学会の論文
著者
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Uehara Akira
Department Of Chemistry Faculty Of Science Kanazawa University
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SUZUKI Masatatsu
Department of Chemistry, Faculty of Science, Kanazawa University
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Sugisawa Toshiharu
Department of Chemistry, Faculty of Science, Kanazawa University
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