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Structural studies of lanthanide nitrate-${it N,N'}$-dimethyl-${it N,N'}$-diphenylpyridine-2,6-dicarboxyamide complexes

${it N,N'}$-dimethyl-${it N,N'}$-diphenylpyridine-2,6-dicarboxyamideの硝酸ランタノイド錯体の構造の研究

藤原 亜佐子 ; 仲野 義晴*; 矢板 毅; 奥野 健二*

Fujiwara, Asako; Nakano, Yoshiharu*; Yaita, Tsuyoshi; Okuno, Kenji*

抽出剤${it N,N'}$-dimethyl-${it N,N'}$-diphenylpyridine-2,6-dicarboxyamide(DMDPhPDA)は放射性廃液から3価のアクチノイド元素とランタノイド元素を選択的に抽出することが期待されている。この抽出のメカニズム解明の一助とするべく、DMDPhPDAとその硝酸ランタン錯体の結晶構造と、DMDPhPDAと硝酸ランタノイドの錯形成定数などを調べた。その結果、DMDPhPDAは2つまでランタノイドイオンの内圏に配位できる可能性が高く、また、外圏に存在するDMDPhPDAと交換していることが示唆された。

The tridentate ligand ${it N,N'}$-dimethyl-${it N,N'}$-diphenylpyridine-2,6-dicarboxyamide (DMDPhPDA) and the corresponding lanthanum complex [La(NO$$_{3}$$)$$_{3}$$(DMDPhPDA)$$_{2}$$] have been prepared and structurally characterised. In the lanthanum complex, two DMDPhPDA molecules coordinated to La(III) in a tridentate fashion and to three nitrate ions in a bidentate fashion make the lanthanum atom 12-coordinate. The stability constants determined by spectrophotometric titration suggest that [Ln(DMDPhPDA)$$_{2}$$]$$^{3+}$$ is the primary product in nitrate media and [Ln(DMDPhPDA)$$_{3}$$]$$^{3+}$$ is difficult to form. However, [Ln(DMDPhPDA)$$_{2}$$]$$^{3+}$$ could not be distinguished in $$^{13}$$C NMR spectra. The $$^{13}$$C NMR titration results imply that a fast ligand exchange process takes place.

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パーセンタイル:64.68

分野:Chemistry, Physical

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