ESR studies on salicylaldehyde Schiff base complexes of copper(II). III. Dimer formation on bis (N-alkylsalicylideneaminato)-copper(II) complexes and their derivatives in toluene.
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概要
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Twenty one of the title complexes (abbreviated as Cu(X–sal–R)<SUB>2</SUB>; X=H, 5-Cl, or 5-Br and R=<I>N</I>-alkyl) in toluene have been extensively studied by the ESR method in order to obtain fundamental information on dimer formability and the dimeric structures of these complexes. The equilibrium constant (<I>K</I>) for 2 monomer \rightleftharpoons dimer has been determined by analyzing the concentration dependence of the intensity ratios of the dimer to the monomer ESR signals for frozen toluene solutions. The <I>K</I> values of the Cu(H–sal–R)<SUB>2</SUB> complexes are remarkably R-dependent as follows: methyl (233)>>ethyl (10)∼isobutyl (9)>other normal alkyl groups (∼4) for a series of the R groups with primary α-carbons, and cyclohexyl (75)>>isopropyl (7)><I>s</I>-butyl (<<1)>cycloheptyl (∼0)><I>t</I>-butyl (0) for a series of the R groups with secondary and tertiary α-carbons, where the complex is denoted by R, followed by <I>K</I> (M<SUP>−1</SUP>) in parentheses. The complexes with R=nonyl or higher homologues form some polymeric species besides dimers and monomers. The <I>K</I> values remarkably increase by the introduction of X=5-Cl or 5-Br. The observed dimer ESR spectra have been analyzed by computer simulation in order to estimate the structural parameters (<I>r</I> and ξ) of parallel-planar dimers, where <I>r</I> is the Cu–Cu distance and ξ is the angle between the Cu–Cu direction and the normal to the molecular plane. These results indicate that most complexes form two types of dimers with different structures: type a, <I>r</I>=3.75 Å and ξ=37°; type b, <I>r</I>=4.10 Å and ξ=23°. The Cu(X–sal–methyl)<SUB>2</SUB> complexes form only a-type dimers, while the others simultaneously form both types of dimers, except the complexes of R=isopropyl and cyclohexyl which form another type of parallel-planar dimers having a slightly tetrahedrally-distorted coordination geometry around each copper atom.
- 公益社団法人 日本化学会の論文
著者
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Yokoi Hiroshi
Department Of Applied Chemistry Faculty Of Engineering Shizuoka University
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Takeuchi Akira
Institute For Materials Research Tohoku University
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Yamada Shoichiro
Institute of Chemistry, College of General Education, Osaka University
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