The formation constants and configurations of the complexes of Cr(II),Mn(II),Fe(II),Co(II),Cu(II),and Zn(II) with 2,2'-bipyridine and of Co(II) with 2,2':6',2"-terpyridine in hexamethylphosphoric triamide.
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概要
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The absorption spectra and the first formation constants, <I>K</I><SUB>19</SUB> of complexes [M(bpy)]<SUP>2+</SUP> (M(II)=Cr(II), Mn(II), Fe(II), Co(II), Cu(II), and Zn(II), bpy=2,2′-bipyridine) were determined spectrophotometrically in hexamethylphosphoric triamide(HMPA). The values of log <I>K</I><SUB>1</SUB> obtained were 4.61±0.02, 3.10±0.12, 4.82±0.04, 5.84±0.07, 7.33±0.02, and 1.77±0.07 for respective metal ions. The configurations of complexes [M(bpy)]<SUP>2+</SUP> were discussed on the basis of these data. The <I>K</I><SUB>1</SUB> values of [Cr(bpy)]<SUP>2+</SUP>, [Mn(bpy)]<SUP>2+</SUP>, [Fe(bpy)]<SUP>2+</SUP>, and [Co(bpy)]<SUP>2+</SUP> in HMPA are slightly larger than those in H<SUB>2</SUB>O, indicating that their configurations are tetrahedral, whereas the value of [Cu(bpy)]<SUP>2+</SUP> in HMPA is slightly smaller than that in H<SUB>2</SUB>O, indicating that its configuration in HMPA is either square planar or tetragonal. It seems that [Zn(bpy)]<SUP>2+</SUP> is octahedral in HMPA, because its <I>K</I><SUB>1</SUB> value is smaller about three orders of magnitude than that in H<SUB>2</SUB>O. In addition, the second formation constant, <I>K</I><SUB>2</SUB>, of complex [Co(bpy)<SUB>2</SUB>]<SUP>2+</SUP>, and the first and second formation constants of complexes [Co(terpy)]<SUP>2+</SUP> and [Co(terpy)<SUB>2</SUB>]<SUP>2+</SUP> (terpy=2,2′:6′,2″-terpyridine) were also determined to be log<I>K</I><SUB>2</SUB>=3.59±0.03 for the bpy complex, and log<I>K</I><SUB>1</SUB>=4.87±0.01 and log<I>K</I><SUB>2</SUB>=3.35±0.01 for the terpy complexes, respectively. These three complexes are concluded to be octahedral.
- 公益社団法人 日本化学会の論文
著者
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Abe Yuriko
Department Of Chemistry Faculty Of Science Nara Women's University
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Wada Goro
Department of Chemistry, Faculty of Science, Nara Women s University
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