Studies on mixed chelates. XIX. 5-coordinate nickel(II) complexes with N,N,N'N",N"-pentamethyldiethylenetriamine and .BETA.-diketonates.
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概要
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Mixed Ni(II) chelates with <I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>″,<I>N</I>″-pentamethyldiethylenetriamine (pmdt) and a β-diketonate (dike) such as acetylacetonate(acac), dipivaloylmethanate(dipm), pivaloyltrifluoroacetonate(pfac), trifluoroacetylacetonate(tfac) or hexafluoroacetylacetonate(hfac) were prepared, and their structure and properites were studied. X-Ray crystal analysis confirmed that [Ni(acac)(pmdt)]ClO<SUB>4</SUB> is a distorted square pyramidal complex, and the solid reflection spectra of the remaining chelates indicated that most of them are also essentially square pyramidal. This structure is retained in a nonpolar solvent like 1,2-dichloroethane, but in strong donor solvents like DMSO or DMF it is converted into a 6-coordinated structure, [Ni(dike)(pmdt)(Solvent)]<SUP>+</SUP>, containing a solvent molecule. The formation of this species is favored by increasing donor number(DN) of the solvent, and in the following order of dike:dipm<acac<<tfac, pfac<<hfac, which is almost opposite to the order of their p<I>K</I><SUB>a</SUB> values.
- 公益社団法人 日本化学会の論文
著者
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OHASHI Yuji
Department of Chemistry and Materials Science Tokyo Institute of Technology
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Sone Kozo
Department Of Chemistry Faculty Of Science Josai University
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Fukuda Yutaka
Department Of Chemistry Faculty Of Science Ochanomizu Univeity
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Ohashi Yuji
Department of Chemistry, Faculty of Science,Tokyo Institute of Technology
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Shintani Noriko
Department of Chemistry, Faculty of Science, Ochanomizu University
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