Linear tetranuclear copper(II) complexes with bridging methoxide and a Schiff-base ligand: The preparation and magnetic study of the [Cu(salpd-.MU.-O,O')(.MU.-L)Cu(.MU.-CH3O)2Cu(.MU.-L)(sapd-.MU.-O,O')Cu] complexes (and L=acetate or formate ions) and the
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概要
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The title complexes have been synthesized in quantitative yield from [Cu(salpd)] and copper(II) acetate or copper(II) formate , where H<SUB>2</SUB>salpd represents <I>N</I>,<I>N</I>′-disalicylidene-1,3-propanediamine. [Cu(salpd-μ-<I>O</I>,<I>O</I>′)(μ-L)Cu(μ-CH<SUB>3</SUB>O)<SUB>2</SUB>Cu(μ-L)(salpd-μ-<I>O</I>,<I>O</I>′)Cu] crystallizes in the monoclinic space group <I>P</I>2<SUB>1</SUB>/<I>n</I> with formula=Cu<SUB>4</SUB>C<SUB>40</SUB>H<SUB>44</SUB>N<SUB>4</SUB>O<SUB>10</SUB>, F.W.=995.0, <I>a</I>=11.826(2) Å, <I>b</I>=17.192(4) Å, <I>c</I>=9.836(2) Å, β=94.08(2)°, <I>V</I>=1994.8(7) Å<SUP>3</SUP> and <I>Z</I>=2 (<I>R</I>=3.83%), where L=CH<SUB>3</SUB>COO. The complex forms a centrosymmetric molecule made up of two units of [Cu(salpd-μ-<I>O</I>,<I>O</I>′)(μ-CH<SUB>3</SUB>COO)Cu] bound by a pair of methoxo bridges; each terminal copper(II) ion forms four short bonds with N and O atoms of salpd and a slightly longer (2.235(4) Å) axial bond with one of the oxygens of the acetato group, whereas each inner copper(II) ion is also pyramidally coordinated by two methoxo oxygens, one of the acetato oxygens, and one of the bridging salpd oxygens, the distant axial position being occupied (Cu–O=2.323(3) Å) by the remaining bridging salpd oxygen. The magnetic susceptibilities of the complexes in the 86.8–299.0 K range have been analyzed on the basis of a four-spin model for the linear copper(II) complexes, and the values of <I>g</I> and <I>J<SUB>ij</SUB></I>, based on the Heisenberg-type Hamiltonian <I>H</I>=−2Σ<I>J<SUB>ij</SUB>S<SUB>i</SUB></I>·<I>S<SUB>j</SUB></I>, have been estimated as <I>g</I> (average)=2.13, <I>J</I><SUB>12</SUB>=−390 cm<SUP>−1</SUP>, <I>J</I><SUB>13</SUB>=67 cm<SUP>−1</SUP> and <I>J</I><SUB>14</SUB>=34 cm<SUP>−1</SUP> in the complex with acetate bridges, and as <I>g</I> (average)=2.20, <I>J</I><SUB>12</SUB>=−263 cm<SUP>−1</SUP>, and <I>J</I><SUB>13</SUB>=39 cm<SUP>−1</SUP> and <I>J</I><SUB>14</SUB>=<I>J</I><SUB>34</SUB>=0 cm<SUP>−1</SUP> in the complex with formate bridges, where the numbering refers to the 3–1–2–4 arrangement of the Cu<SUP>2+</SUP> ions.
- 公益社団法人 日本化学会の論文
著者
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Matsumoto Naohide
Department Of Chemistry Faculty Of Science Kumamoto University
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Kida Sigeo
Department of Chemistry Wakayama University
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Katsura Kosho
Department Of Chemistry College Of Science University Of The Ryukyus
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Mori Masayasu
Department of Chemistry, Faculty of Science, Osaka City University
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Fukuhara Ch\={o}ki
Department of Chemistry, College of Science, University of the Ryukyus
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Tsuneyoshi Kazuhiko
Department of Chemistry, College of Science, University of the Ryukyus
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