NMRによるCMPO/TBP系におけるランタニド錯体の構造解析(II)

Study of lanthanide (III) nitrate complexes in CMPO/TBP systems by nuclear magnetic resonance (II)

佐野 雄一   ; 青瀬 晋一*; 岡本 文敏; 狩野 純一*; 小山 智造; 田中 康正

Sano, Yuichi; not registered; not registered; not registered; Koyama, Tomozo; Tanaka, Yasumasa

TRUEXプロセスにおいて使用される抽出剤CMPO(octyl(phenyl)-N,N-diisobutylCarbamoylMethylPhosphineOxide)及び相改質剤TBP(Triisobutylphosphate)と軽ランタニド元素(La,Ce,Pr,Nd,Sm,Eu)との反応について、NMR(NuclearMagneticResonance;核磁気共鳴吸収)測定を用いて検討を行った。NMR測定の結果から、ランタニド(Ln)/CMPO/TBP系におけるLn錯体の構造について、系内のLn3+イオンに対するCMPOの濃度比により、以下に示すような変化をすることが確認された。Ln/CMPO/TBP系([CMPO]/[Ln](モル濃度比)3)硝酸イオン-Ln/TBP系と類似の配位様式CMPO,TBP-ともに配位(複数の配位様式)Ln/CMPO/TBP系([CMPO]/[Ln](モル濃度比)3)硝酸イオン-Ln/CMPO系と類似の配位様式CMPO,TBP-CMPOのみが2座配位(Ln/CMPO系と同様の配位様式)TBPは第一配位圏外に存在し、Ln-CMPO錯体のCMPO交換反応に寄与

The coordination properties of the lanthanide (La, Ce, Pr, Nd, Sm and Eu) complexes in lanthanide/TBP (tributylphosphate), lanthanide/CMPO (octyl(phenyl)-N,N-diisobutycarbamoylmethylphosphine oxide) and lanthanide/CMPO/TBP systems were investigated by NMR (nuclear magnetic resonance) measurements. In the lanthanide/CMPO/TBP system, it is shown that the structure of lanthanide complex is changed by the concentration ratio for added CMPO to the lanthanide ion ; lanthanide/CMPO/TBP system ([CMPO]/[Ln] 3 (mole ratio)) NO - the similar coordination in the Ln/TBP system TBP, CMPO - These coordinate to the lanthanide ion together. (the existence of several complexes) lanthanide/CMPO/TBP system ([CMPO]/[Ln} 3(mole ratio)) NO - the same coordination in the Ln/CMPO system TBP, CMPO - Only CMPO coordinates to the lanthanide ion. TBP doesn't exist within the first coordination sphere, but affects the CMPO exchange reaction.