Binuclear metal complexes. XLV. Synthesis and magnetic, spectral, and electrochemical studies of strati-bis copper(II) complexes of some Schiff bases derived from primary tetraamines and salicylaldehydes.
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概要
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New Schiff base ligands, 1,2,3,4-tetrakis(R-salicylideneamino)-2,3-dimethylbutane (abbreviated as H<SUB>4</SUB>(R-sata); R (substituent on the ring)=H, 5-Me, 5-Bu<I><SUP>t</SUP></I>) and 1,2-bis(R-salicylideneamino)-1,2-bis(salicylideneaminomethyl)cyclohexane (H<SUB>4</SUB>(R-sacta)), which are capable of forming "strati-bis" type binuclear copper(II) complexes, have been synthesized. Magnetic, spectral and electrochemical properties of the binuclear copper(II) complexes, Cu<SUB>2</SUB>(R-sata) and Cu<SUB>2</SUB>(R-sacta), were investigated in comparison with those of mononuclear copper(II) complexes Cu(R-salpn) and Cu(R-sacda), where H<SUB>2</SUB>(R-salpn) is <I>N</I>,<I>N</I>′-bis(R-salicylidene)-1,2-propanediamine and H<SUB>2</SUB>(R-sacda) 1-(R-salicylideneamino)-1-(R-salicylideneaminomethyl)cyclohexane. ESR spectra of Cu<SUB>2</SUB>(sata), Cu<SUB>2</SUB>(sacta) and Cu<SUB>2</SUB>(5-Me-sacta) showed a seven-lined hyperfine structure whose hyperfine coupling constant (<I>A</I><SUB>||</SUB>≈85 G, 1 G=10<SUP>−4</SUP> T) was about one half of that of the corresponding mononuclear copper(II) complex. Each electronic spectrum of these binuclear complexes showed the π-π<SUP>*</SUP> transition originated from the azomethine group at a low frequency compared with that of the corresponding mononuclear complex. Cyclic voltammograms of these three complexes involved two redox couples. The first redox couple attributable to the Cu(II, II)/Cu(II,I) process is higher in potential than the Cu(II)/Cu(I) process of the corresponding mononuclear complex. These characteristics were discussed in terms of the electron-delocalization through the π-π interaction between the two [CuN<SUB>2</SUB>O<SUB>2</SUB>]-chromophores.
- 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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Izumitani Tatsuo
Department of Chemistry, Faculty of Science, Kyushu University 33
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