Binuclear metal complexes. XLIII. Magnetic, spectroscopic, and electrochemical studies on hetero-metal binuclear complexes of N,N'-bis(3-carboxysalicylidene)-1,1-dibenzylethylenediamine.
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概要
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Copper(II)–M(II) and copper(II)–iron(III) hetero-metal binuclear complexes of <I>N</I>,<I>N</I>′-bis(3-carboxysalicylidene)-1,1-dibenzylethylenediamine (H<SUB>4</SUB>fsadb), CuM(fsadb)·<I>n</I>H<SUB>2</SUB>O (M=Co, Ni, Cu, Zn, Mg, Ca, Ba) and CuFe(fsadb)Cl·1.5H<SUB>2</SUB>O, have been prepared and characterized. Cryomagnetic measurements (78–300 K) revealed that an antiferromagnetic spin-exchange interaction operates between the metal ions in the cases CuM(fsadb)·<I>n</I>H<SUB>2</SUB>O (M=Co, Ni, Cu) and CuFe(fsadb)Cl·1.5H<SUB>2</SUB>O, exchange integrals being evaluated on the basis of the Heisenberg model. Ligand field bands due to the copper(II) ion bound at the N<SUB>2</SUB>O<SUB>2</SUB>-site of CuM(fsadb)·<I>n</I>H<SUB>2</SUB>O (M=Co, Ni, Cu, Zn, Mg) and CuFe(fsadb)Cl·1.5H<SUB>2</SUB>O are in the range 1.9×10<SUP>3</SUP>–21.4×10<SUP>3</SUP> cm<SUP>−1</SUP>, while in the cases of CuCa(fsadb)·4H<SUB>2</SUB>O and CuBa(fsadb)·3.5H<SUB>2</SUB>O the frequencies of the bands are close to that (17.8×10<SUP>3</SUP> cm<SUP>−1</SUP>) of the mononuclear complex Cu(H<SUB>2</SUB>fsadb)·H<SUB>2</SUB>O. This spectral feature has been explained in terms of the configuration of the second metal ion adjacent to the copper(II) ion: <I>trans</I>-octahedral in the cases of small metal ions (Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mg(II)) and presumably <I>cis</I>-octahedral in the cases of large metal ions (Ca(II), Ba(II)). Copper(II/I) redox potentials of the hetero-metal complexes are much low compared with that of Cu(H<SUB>2</SUB>fsadb)·H<SUB>2</SUB>O. This shift has been discussed in terms of the electronic effect of the carboxylate group and the covalency in the bonding between the bridging phenolic oxygen and the second metal ion.
- 公益社団法人 日本化学会の論文
著者
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Okawa Hisashi
Department Of Chemistry Faculty Of Science Kyushu University
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Nakamura Masaaki
Department Of Applied Physics Faculty Of Science Tokyo University Of Science
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Kida Sigeo
Department of Chemistry Wakayama University
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Kanda Wakako
Department of Chemistry, Faculty of Science, Kyushu University
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